Two-photon fluorescent dye based on 4-methoxyphenyl-substituted BODIPY and diphenylaminofluorene and synthesis method of two-photon fluorescent dye

A fluoroboron-substituted dipyrrole, two-photon fluorescence technology, applied in the field of fluorescent dyes, can solve the problem of insignificant improvement of the two-photon absorption cross-section, achieve good single-photon and two-photon absorption and fluorescence performance, improve the two-photon absorption cross-section, The effect of high synthesis yield

Active Publication Date: 2017-02-22
CHINA NAT TOBACCO QUALITY SUPERVISION & TEST CENT
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Problems solved by technology

For example, Wang et al. introduced alkynyl electron-donating groups at the 2 and 6 positions of fluoroboron dipyrrole, but the improvement of its two-photon absorption cross section was not obvious (29-60 GM) [6]

Method used

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  • Two-photon fluorescent dye based on 4-methoxyphenyl-substituted BODIPY and diphenylaminofluorene and synthesis method of two-photon fluorescent dye
  • Two-photon fluorescent dye based on 4-methoxyphenyl-substituted BODIPY and diphenylaminofluorene and synthesis method of two-photon fluorescent dye
  • Two-photon fluorescent dye based on 4-methoxyphenyl-substituted BODIPY and diphenylaminofluorene and synthesis method of two-photon fluorescent dye

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0025] Example 1: Synthesis of 2,6-iodofluoroboron dipyrrole fluorophore 1a

[0026] Under argon protection, add 500 mL of dichloromethane, 18.9 mmol of 2,4-dimethylpyrrole, 7.6 mmol of 4-methoxybenzaldehyde and three drops of trifluoroacetic acid as catalysts into a 1000 mL three-neck flask, and stir magnetically at room temperature After 6 h, 7,9 mmol of 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) was dissolved in 150 mL of dichloromethane, added to the above reaction solution, and continued to stir at room temperature for 15 min. Then, 10 mL of diisopropylethylamine (DIEA) and 10 mL of boron trifluoride ether solution were added to the above reaction liquid, and after stirring at room temperature for 30 min, 200 mL of water was added to quench the reaction, dichloromethane was extracted, and the liquids were separated. , dried over anhydrous sodium sulfate, the solvent dichloromethane was distilled off in vacuo, using dichloromethane:petroleum ether=1:2 as the eluent, and se...

Embodiment 2

[0028] Embodiment 2: the synthesis of diphenylamine-fluorene-acetylene compound 2e (R=C 2 h 5 )

[0029] (1) Synthesis of 2a

[0030] In a 250 mL round bottom flask, dissolve 5 g of fluorene into 50 mL of dry chloroform, dissolve 4.18 mL (2.74 times) of liquid bromine in 30 mL of dry chloroform solution, and in a constant pressure dropping funnel at 0 °C Add the above mixture dropwise to the reaction flask. Stirring overnight under dark conditions, the saturated Na 2 S 2 o 3 Add the solution to the reaction solution to neutralize the excess liquid bromine, quench the reaction, separate the layers, wash the organic layer with water several times, and add anhydrous MgSO to the organic phase 4 After drying for half an hour, anhydrous magnesium sulfate was removed by filtration, the solvent was removed by vacuum rotary evaporation, and recrystallized in ethanol to obtain a white solid 2a with a yield of 95%.

[0031] (2) Synthesis of 2b

[0032] Add 5 g of 2,7-dibromofluor...

Embodiment 3

[0039] Embodiment 3: the synthesis of two-photon fluorescent dye TPFD (R=C 2 h 5 )

[0040] In a 10 mL Shrek reaction tube, add compound 2e (0.11 g, 0.26 mmol), Pd 2 (dba) 3 (4.58mg, 5%), tris(2-furyl)phosphine (2.32 mg, 10%) and CuI (1.9 mg, 10%), then add 0.8 mL of anhydrous N,N-dimethylformamide (DMF ) and 0.2 mL of freshly treated triethylamine, add compound 1a ( 0.1 mmol) under nitrogen protection, seal the reaction bottle, and react at 60 °C for 0.5 h, TLC board detection raw material fluoroborate dipyrrole reaction is complete Finally, stop the reaction, pour the reaction solution into ether, transfer to a separatory funnel, wash with water several times, let stand to separate layers, and wash the collected upper organic phase with anhydrous MgSO 4 Dry, filter with Buchner funnel to remove anhydrous magnesium sulfate, evaporate and concentrate in vacuo, dissolve the resulting blue solid in dichloromethane, and adsorb onto silica gel, using petroleum ether:dichlorom...

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Abstract

The invention provides a two-photon fluorescent dye based on 4-methoxyphenyl-substituted BODIPY and diphenylaminofluorene and a synthesis method of the two-photon fluorescent dye. The structural formula of the two-photon fluorescent dye is shown in the specification, wherein R is C1-C18 alkyl. The synthesis method of the synthesized two-photon fluorescent dye comprises steps as follows: (1) 2,6-bit iodinated BODIPY is prepared from 2,4-dimethyl pyrrole and 4-methoxybenzaldehyde as raw materials; (2) fluorene as a raw material is subjected to bromination, alkylation, Pd (0) catalytic amination, Pd (0) and CuI catalysis and the like, and a diphenylamine-fluorene-acetylene compound is produced; (3) the two products react, and the two-photon fluorescent dye is obtained. The synthesized target compound has higher two-photon fluorescent performance; in the toluene, the maximum two-photon absorption cross section of the compound reaches 615 GM and the fluorescence quantum yield is 0.39; a new design idea is provided for synthesis and application of the two-photon fluorescent dye based on BODIPY.

Description

technical field [0001] The invention belongs to the technical field of fluorescent dyes, and in particular relates to a two-photon fluorescent dye based on 4-methoxyphenyl substituted fluoroboron dipyrrole and dianilinofluorene and a synthesis method thereof. Background technique [0002] Two-photon absorption is a third-order nonlinear optical effect. Organic materials with large two-photon absorption cross-sections in three-dimensional optical storage [1] , two-photon fluorescence imaging [2] , two-photon optical limiting material [3] and photodynamic therapy [4] and other fields have broad application prospects. In the research field of two-photon fluorescent dyes, the development of fluorescent dyes with larger two-photon absorption cross section is the key. [0003] Fluoroboron dipyrrole is a class of fluorescent chromophores with excellent performance. It has a large molar extinction coefficient, high fluorescence quantum yield, good photostability, good toleran...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02C09K11/06C09B57/00
CPCC07F5/022C09B57/00C09K11/06C09K2211/1007C09K2211/1011C09K2211/1029C09K2211/1055
Inventor 韩书磊陈欢刘彤付亚宁侯宏卫
Owner CHINA NAT TOBACCO QUALITY SUPERVISION & TEST CENT
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