Preparation method and application of fluorescent dye of carbazole-rhodamine hybrid structures

Abstract

The invention provides a preparation method and application of fluorescent dye of carbazole-rhodamine hybrid structures. The method has the advantages that the designed and synthesized novel carbazole-rhodamine fluorescent dye sufficiently uses the various good properties of carbazole in the field of a photoelectric material as a structure base element and good optical physical and optical chemical properties of rhodamine dye. Through such a hybrid design, the dye shows a greater molar absorption coefficient, longer fluorescence emission wavelength, more flexible and controllable adsorption and fluorescence emission wavelength and the like than the carbazole base element structure. A fluorescence probe designed and synthesized by using the hybridization dye has good selectivity on copper ions; the primary application value of the dye is shown.

Description

Technical field

[0001] The invention relates to the preparation of fluorescent dyes in photoelectric devices and optical sensing imaging detection technologies, in particular to a preparation method and application of fluorescent dyes based on a carbazole-rhodamine hybrid structure.

Background technique

[0002] In recent years, fluorescence analysis technology has gradually become an important method in modern analysis technology. Because of its high sensitivity and selectivity, it has become an important method in the identification, detection and monitoring of some important substances in biology, environment and medicine. The main application direction. Although some conventional detection methods such as high-resolution liquid chromatography, mass spectrometry, atomic absorption spectroscopy, inductively coupled plasma atomic emission spectroscopy, and electrochemical sensing have been used for the analysis of related substances, these detection methods have complex...

Examples

Embodiment 1

[0023] Embodiment 1, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0024] The preparation steps are as follows:

[0025] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid (3.14g, 10mmol) into 60mL of methanesulfonic acid and stir in 60°C oil The reaction was heated in a bath for 5 hours, and then heated in an oil bath at 80° C. for 10 hours to obtain a product solution.

[0026] 2) Add 600mL water to the reacted product solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4 After drying and filtering, the obtained solid crude product was passed through a silica gel column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.31 g of powder white solid powder, yield 72%, melting point: 238-242 ℃.

[0027] 1 H NMR (400MHz, CDCl 3 )δ=8.23(d,J=6....

Embodiment 2

[0028] Embodiment 2, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0029] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid (3.46g, 11mmol) into 50mL methanesulfonic acid and stir, 65°C oil The reaction was heated in a bath for 5 h, and then heated in an oil bath at 85° C. for 5 h.

[0030] 2) Add 600mL water to the reaction solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4After drying and filtering, the obtained solid crude product was passed through a silica gel chromatography column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.12 g of off-white solid powder, and the yield was 67.8%. Melting point: 238-242°C. Progen spectrum and carbon spectrum are the same as embodiment 1.

Embodiment 3

[0031] Embodiment 3, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0032] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid (3.76g, 12mmol) into 50mL of methanesulfonic acid and stir in 80°C oil The reaction was heated in a bath for 10 h, and then heated in an oil bath at 95° C. for 5 h.

[0033] 2) Add 600mL water to the reaction solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4 After drying and filtering, the obtained solid crude product was passed through a silica gel chromatography column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.22 g of powdery white solid powder, and the yield was 70.0%. Melting point: 238-242°C. Progen spectrum and carbon spectrum are the same as embodiment 1.

Technical field

[0001] The invention relates to the preparation of fluorescent dyes in photoelectric devices and optical sensing imaging detection technologies, in particular to a preparation method and application of fluorescent dyes based on a carbazole-rhodamine hybrid structure.

Background technique

[0002] In recent years, fluorescence analysis technology has gradually become an important method in modern analysis technology. Because of its high sensitivity and selectivity, it has become an important method in the identification, detection and monitoring of some important substances in biology, environment and medicine. The main application direction. Although some conventional detection methods such as high-resolution liquid chromatography, mass spectrometry, atomic absorption spectroscopy, inductively coupled plasma atomic emission spectroscopy, and electrochemical sensing have been used for the analysis of related substances, these detection methods have complex...

Examples

Embodiment 1

[0023] Embodiment 1, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0024] The preparation steps are as follows:

[0025] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid (3.14g, 10mmol) into 60mL of methanesulfonic acid and stir in 60°C oil The reaction was heated in a bath for 5 hours, and then heated in an oil bath at 80° C. for 10 hours to obtain a product solution.

[0026] 2) Add 600mL water to the reacted product solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4 After drying and filtering, the obtained solid crude product was passed through a silica gel column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.31 g of powder white solid powder, yield 72%, melting point: 238-242 ℃.

[0027] 1 H NMR (400MHz, CDCl 3 )δ=8.23(d,J=6....

Embodiment 2

[0028] Embodiment 2, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0029] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl) benzoic acid (3.46g, 11mmol) into 50mL methanesulfonic acid and stir, 65°C oil The reaction was heated in a bath for 5 h, and then heated in an oil bath at 85° C. for 5 h.

[0030] 2) Add 600mL water to the reaction solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4After drying and filtering, the obtained solid crude product was passed through a silica gel chromatography column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.12 g of off-white solid powder, and the yield was 67.8%. Melting point: 238-242°C. Progen spectrum and carbon spectrum are the same as embodiment 1.

Embodiment 3

[0031] Embodiment 3, the preparation of carbazole-rhodamine hybrid fluorescent dye 1

[0032] 1) Add 2-hydroxycarbazole (1.83g, 10mmol) and 2-(4-diethylamino-2-hydroxybenzoyl)benzoic acid (3.76g, 12mmol) into 50mL of methanesulfonic acid and stir in 80°C oil The reaction was heated in a bath for 10 h, and then heated in an oil bath at 95° C. for 5 h.

[0033] 2) Add 600mL water to the reaction solution, add appropriate amount of NaHCO 3 The solid neutralized the reaction solution, extracted with dichloro to collect the organic phase, and washed with anhydrous Na 2 SO 4 After drying and filtering, the obtained solid crude product was passed through a silica gel chromatography column with dichloromethane and ethyl acetate to obtain carbazole-rhodamine hybrid fluorescent dye 1, 3.22 g of powdery white solid powder, and the yield was 70.0%. Melting point: 238-242°C. Progen spectrum and carbon spectrum are the same as embodiment 1.

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