Bithiophene-biscoumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof

A technology of dicoumarin and fluorescent dyes, which is applied in the synthesis of organic compounds, functional fluorescent dyes and fine chemicals, can solve the problems of low selectivity, immature reaction, and many synthesis steps, and achieve high selectivity and synthetic methods Effect of mature, high molar extinction coefficient

Inactive Publication Date: 2021-06-22
NANJING FORESTRY UNIV
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0005] Based on the easy modification of BODIPY-based fluorescent dye precursors, the excellent photophysical properties of coumarin derivatives, and the superior photoelectric properties of thiophene, a bisthiophene-biscoumarin-based BODIPY was synthesized by Knoevenagel condensation and Sonogashira coupling reactions Similar to near-infrared fluorescent dyes, avoiding the problems of many near-infrared fluoroboron-dipyrrole dyes, such as many synthesis steps, immature reactions, and low selectivity

Method used

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  • Bithiophene-biscoumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof
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  • Bithiophene-biscoumarin-based BODIPY near-infrared fluorescent dye and preparation method thereof

Examples

Experimental program
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Effect test

Embodiment 1

[0026] The preparation of embodiment 1 dicoumarin base BODIPY derivative (II)

[0027] Under anhydrous conditions, in a dry round-bottomed flask equipped with a Dean-Stark apparatus, diiodo-BODIPY derivative (I) (618 mg, 1 mmol), 7-(N,N-diethylamino)coumarin -3-Formaldehyde (735mg, 3mmol) and p-toluenesulfonic acid (86mg, 0.5mmol) were dissolved in 25mL of toluene and 2mL of piperidine, heated to reflux at 125°C, and reacted for 6 hours. Cool to room temperature, extract with dichloromethane, wash with water, combine the organic layers, evaporate the organic solvent under reduced pressure, the residue is separated and purified by silica gel column chromatography, the eluent is 100% dichloromethane, and the gray-brown solid product 3 is obtained. 5-Dicoumarinyl BODIPY derivative (II) (375 mg, 35%). 1 HNMR (600MHz, CDCl 3 ): δ8.38-8.03(m, 2H), 8.00-7.86(m, 2H), 7.85-7.50(m, 2H), 7.41(t, J=8.4Hz, 2H), 6.99(d, J=9.0 Hz, 2H), 6.69(d, J=55.8Hz, 2H), 6.54(dd, J=19.8, 2.4Hz, 2H), 3...

Embodiment 2

[0028] The preparation of embodiment 2 bisthiophene-dicoumarin base BODIPY derivatives (III)

[0029] Under argon protection, 3,5-dicoumarin-based BODIPY derivative (II) (536 mg, 0.50 mmol), Pd(PPh 3 ) 4 (58mg, 0.05mmol), CuI (10mg, 0.05mmol) were dissolved in 30mL tetrahydrofuran and 10mL triethylamine, and then 2-ethynylthiophene (0.15mL, 1.5mmol) was added. The mixture was slowly heated to 60°C and stirred overnight. Cool to room temperature, extract with dichloromethane, wash with water, dry, evaporate the organic solvent under reduced pressure, the residue is separated and purified by silica gel column chromatography, the eluent is 100% dichloromethane, and the gray solid product dithiophene-bicoumarin is obtained Sulfosyl BODIPY derivative (III) (232mg, 45%). 1 H NMR (600MHz, CDCl 3 ): δ8.63(s, 2H), 8.05(s, 2H), 7.86-7.84(d, J=15.0Hz, 2H), 7.54(s, 2H), 7.43-7.42(d, J=6.0Hz, 2H), 7.29(s, 2H), 7.03(s, 2H), 7.00(s, 2H), 6.61(s, 2H), 6.49(s, 2H), 3.47(s, 8H), 2.38(s, 3H...

Embodiment 3

[0030]Example 3 Bithiophene-Dicoumarin-based BODIPY Derivatives (III) Solution UV-Vis Absorption Spectrum

[0031] Dissolve the bisthiophene-dicoumarin-based BODIPY derivative (III) in dichloromethane to a concentration of 1×10 - 5 mol / L dichloromethane solution, and measure its UV-Vis absorption spectrum. figure 1 The ultraviolet-visible absorption spectrum of the near-infrared fluorescent dye (III) solution prepared in Example 2 of the present invention.

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Abstract

The invention relates to a bithiophene-biscoumarin-based BODIPY near-infrared fluorescent dye and a preparation method thereof, and the preparation method is realized by the following steps: carrying out Knoevenagel condensation reaction on a diiodo BODIPY derivative (I) and 7-(N, N-diethylamino) coumarin-3-formaldehyde to obtain a 3, 5-biscoumarin-based BODIPY derivative (II), and then carrying out Sonogashira coupling reaction of the 3, 5-biscoumarin-based BODIPY derivative (II) with 2-acetylene thiophene, so as to obtain the bithiophene-biscoumarin-based BODIPY derivative (III). The preparation method has the advantages of simple reaction steps, mild reaction conditions and good selectivity. The fluorescent dye has excellent photophysical properties such as high molar extinction coefficient (greater than 3.0 * 10 < 5 > cm <-1 > mol <-1 > L), large Stokes shift, good light stability and the like. The strongest electron absorption spectrum red shift is 770nm, the maximum fluorescence emission wavelength is 818nm, and the fluorescent dye has a good application prospect in the fields of optical imaging, fluorescence identification, tumor diagnosis, military reconnaissance, infrared camouflage, organic photovoltaic materials and the like.

Description

technical field [0001] The invention belongs to the technical fields of organic compound synthesis, functional fluorescent dyes and fine chemicals, and specifically relates to a bisthiophene-bicoumarin-based BODIPY near-infrared fluorescent dye and a preparation method thereof. Background technique [0002] Because near-infrared light has little interference during propagation and good permeability to substances, especially in this spectral region, the absorption and fluorescence of biomolecules themselves are the smallest, and with the increase of wavelength, it can avoid the scattering of light by organisms and The bias effect caused by autofluorescence on the detection results, the scattering interference is also greatly reduced, and it has the advantages of strong permeability to tissue cells. In recent years, near-infrared dye molecules have played a significant role in many fields such as optical imaging, tumor diagnosis, military reconnaissance, infrared camouflage, n...

Claims

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Application Information

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IPC IPC(8): C07F5/02C09B57/02C09K11/06
CPCC07F5/022C09K11/06C09B57/02C09K2211/1055C09K2211/1088C09K2211/1092
Inventor 徐海军李鹏飞宋宇婷蔡正春付博
Owner NANJING FORESTRY UNIV
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