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Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof

A technology of dipyrromethene and boron bisfluoride, applied in the field of boron bisfluoride complexed dipyrromethene derivatives, achieving the effect of high comprehensive yield and low cost

Active Publication Date: 2016-02-24
江苏博凡科精密五金科技有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0003] In recent years, researchers have synthesized tens of thousands of new BODIPY dyes with excellent performance by modifying each site of the BODIPY matrix. It has been reported that this is because when a variety of functional groups are introduced into the middle of the BODIPY core, it is difficult to form effective conjugation with the fluorine-boron core plane due to steric hindrance.

Method used

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  • Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof
  • Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof
  • Bridged bis-boron-dipyrromethene (BODIPY) derivative containing fluorene at meso-position and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0080] Synthesis of BDP1

[0081] Add vacuum-dried 9,9'-dibutyl-2,7-dipyrromethene fluorene (285mg, 0.5mmol) and tetrachlorobenzoquinone (250mg, about 1mmol) to a 100ml three-necked flask, in dichloromethane The solution was oxidized with magnetic stirring at room temperature for 8 hours, and the solution in the three-neck flask changed from dark yellow to dark red. Then put the reaction on N 2 Under the protective device, boron trifluoride diethyl ether (4mL, 28mmol) was slowly added dropwise, and triethylamine (4mL, 28mmol) was added in portions after 5min, and the reaction was continued for 4h, and the reaction was stopped. Wash with anhydrous ether and water successively, and dry the organic phase with anhydrous magnesium sulfate. The solvent was spun off under reduced pressure, and the crude product was subjected to silica gel column chromatography with a developer of dichloromethane:petroleum ether=1:1 to obtain 278 mg of a bright yellow solid with a yield of 87% and a...

Embodiment 2

[0083] Synthesis of BDP2

[0084] Using a method similar to the synthesis of BDP1, 2,7-bis[4-(dipyrrolemethyl)phenyl]-9,9-dibutylfluorene was oxidized by TCQ, and reacted with boron trifluoride ether to obtain the target product BDP2, 82% yield, melting point >320°C. 1 HNMR (400MHz, CDCl 3 ,TMS,ppm):δ:7.98(s,4H),7.88-7.86(m,6H),7.68-7.72(m,8H),7.05-7.06(d,J=2.7Hz,4H),6.59(s ,4H),2.10-2.14(t,J=6.8Hz,4H),1.12-1.15(m,8H),0.71-0.74(t,J=7.2Hz,6H); 13 CNMR (100MHz, CDCl 3,TMS,ppm):δ:150.70,147.61,144.16,144.07,138.92,134.56,131.57,131.49,131.26,127.16,126.36,121.54,120.53,118.56,55.23,40.30,29.70,26.13,23.08,13.83.MALDI- TOF-MS, m / z:calcdforC 51 h 44 B 2 f 4 N 4 [M-F] + :791.409,found:791.246.

Embodiment 3

[0086] Synthesis of BDP3

[0087] According to the method of synthesizing BDP2, the compound 2,7-bis[4-(dipyrrolemethyl)phenyl]-9,9-dioctylfluorene (0.5g, 0.6mmol), tetrachloro Benzoquinone and dry dichloromethane were fully oxidized for 6 hours with magnetic stirring at room temperature. Then exhaust the air in the reaction system, pass it into argon protection, slowly add triethylamine dropwise through a syringe, and then use a syringe to take boron trifluoride ether and add it dropwise. The drop rate of boron diethyl ether, after the dropwise addition, continued the magnetic stirring reaction for 4h. The reaction was stopped, and the reaction mixture was poured into NaOH aqueous solution (200 mL, 0.1 M), extracted several times with dichloromethane, washed with water three times, and the organic phases were combined and dried overnight over anhydrous sodium sulfate. The filtrate was collected by filtration, the solvent was evaporated under reduced pressure, and the residu...

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Abstract

The invention discloses a bridged double-center BODIPY derivative containing fluorene at a meso-position and a preparation method thereof. The preparation method comprises the following steps: synthesizing a symmetric dialdehyde compound containing bridging groups consisting of benzene, thiophene and furan and different substituent groups like a butyl group and an octyl group; then subjecting the symmetric dialdehyde compound and pyrrole to a reaction under the catalysis of indium trichloride so as to synthesize a bis(dipyrrolidine) compound; and successively carrying out oxidation by chloranil and fluoroboronation by boron trifluoride ether so as to obtain a fluorene-containing different bridging group-substituted BODIPY dye which has a structural general formula as shown in a formula I that is described in the specification. According to the invention, fluorene and the bridging groups consisting of benzene, thiophene and furan are introduced for the first time and conventional synthetic methods are improved, so the obtained double-center BODIPY dye has stable spectral absorption; and introduction of thiophene, furan and fluorene enables the fluorescence emission peak of the derivative presents obvious red shift, and fluorescence effect is enhanced with enhancement of system conjugative effect. The organic dye can be efficiently synthesized and widely used in fields like life science, analytical chemistry and environmental energy.

Description

Technical field: [0001] The invention relates to the technical field of boron bisfluoride complexed dipyrromethene derivatives, in particular to a boron bisfluoride complexed dipyrromethene derivative with a fluorene bridge in the middle. Background technique: [0002] Boron fluoride complexed dipyrromethene (BODIPY for short) fluorescent dyes have high photostability and strong spectral absorption, and have been widely used in life science, medicine, environmental energy science and other fields. [0003] In recent years, researchers have synthesized tens of thousands of new BODIPY dyes with excellent performance by modifying each site of the BODIPY matrix. It has been reported that this is because when a variety of functional groups are introduced into the middle of the BODIPY core, it is difficult to form an effective conjugation with the fluorine-boron core plane due to steric hindrance. In order to further study the effects of different substituents and bridging groups...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07F5/02C09B57/00C09K11/06
Inventor 赵鸿斌张文涛王育才廖俊旭彭敏戴康徐刘旺谢靖飞
Owner 江苏博凡科精密五金科技有限公司
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