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Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof

A technology of fluoroboridipyrrole and fluorescent dyes, which is applied in the field of near-infrared fluoroboridipyrrole fluorescent dyes and its preparation, can solve the problems of high activity and instability at the alfa position, complex synthesis methods, and low yields, and achieve excellent photophysical The effects of chemical properties, excellent product spectral properties, and high fluorescence quantum yield

Inactive Publication Date: 2014-07-30
ANHUI NORMAL UNIV
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  • Abstract
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Problems solved by technology

However, the main problem is that the preparation involves a reverse D-A reaction, which requires a high temperature of 220 ° C, and the common functional groups are not compatible; the raw materials in the synthesis route B are unstable due to the high activity of the alfa position
The raw material pyrrole derivatives in synthetic route C involve complex total synthesis of specific pyrrole molecules, and the types of synthetic routes are limited (Uppal, T.; Hu, X.; Fronczek, F.R. Chem. Eur. J. 2012, 18, 3893-3905) ; Haugland and Kang adopt synthetic route D phthalic dicarbonyl compound and hydroxylamine reaction, obtain isoindole dimethylene, coordination obtains symmetrical isoindole BODIPY fluorescent dye [Haugland, R.P.; Kang, H.C.US5433896A, US08 / 246,790,1995 ], but the synthesis of phthalic dicarbonyl compounds involves lead tetraacetate, which pollutes the environment seriously, and there are problems in sewage discharge
[0006] The current synthesis method is complicated (expensive raw materials, harsh reaction conditions, low yield), and the types are limited; it is difficult to commercialize

Method used

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  • Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof
  • Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof
  • Near-infrared fluorine-boron dipyrrole fluorochrome and preparation method thereof

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0049] Synthesis of Dye 2-2a:

[0050]

[0051] Weigh 400 mg of imine, 532 mg of 3-methoxyphenylboronic acid (2.2e.q.) into a 100 mL Slack reactor, add 15 mL of toluene, 10 mL of 1M Na 2 CO 3 Solution, 2mL ethanol, after solidification in liquid nitrogen environment, vacuumize, argon flow, repeat three times, add catalyst Pd(PhP 3 ) 4 60 mg, vacuum again, argon, repeat three times. After the reactor returned to room temperature, it was placed in an 80°C oil bath and heated for 12h. Point the plate, the imine reaction is complete, and the reaction is over. It was extracted with ethyl acetate, concentrated, and passed through the column to obtain 335 mg of 1-1 yellow powder with a yield of 83.8%. 1 H NMR (300MHz, CDCl 3 )δ9.91(s, 1H), 8.02(t, J=4.8Hz, 2H), 7.50-7.37(m, 4H), 7.26(t, J=7.5Hz, 1H), 7.02(d, J=7.2 Hz,1H),3.92(s,3H); 13 CNMR (75MHz, CDCl 3 )δ173.9,161.0,130.5,127.5,124.4,124.0,122.1,122.0,121.9,120.0,117.6,115.2,115.1,112.9,112.8,55.5.HRMS(ESI)calcd.for C ...

Embodiment 2

[0054]

[0055] Weigh 400 mg of imine, 532 mg of 4-methoxyphenylboronic acid (2.2e.q.), and repeat the above operation to obtain 350 mg of 2-1b yellow powder with a yield of 87.5%. 1 H NMR (300MHz, CDCl3 )δ9.87(s,1H),7.98(d,J=6.9Hz,2H),7.77(d,J=8.1Hz,2H),7.41(s,1H),7.26(s,1H),7.10- 7.07(m,2H),3.90(s,3H); 13 CNMR (75MHz, CDCl 3 )δ173.0,160.4,135.8,135.7,133.2,133.1,129.5,127.4,123.9,123.5,123.0,122.1,121.8,117.4,114.6,55.4. HRMS(ESI)calcd.for C 16 h 13 NO 2 [M+H] + :252.1019,found252.1019.

[0056] In a 50 mL round bottom flask, add 20 mL of CH under argon 2 Cl 2 , add aldehyde (90 mg, 0.5 mmol), and add POCl which has been dissolved in 1 mL of dichloromethane 3 (0.47ml, 5mmol), the solution immediately changed from light yellow to yellow-green and then to green, and the color gradually deepened as the reaction time increased. After reacting for 4 hours, add 1.0 mL of diisopropylamine at room temperature, stir at room temperature for 10 minutes, add 1.2 mL of boron ...

Embodiment 3

[0058]

[0059] Weigh 400 mg of imine and 624 mg of 4-tert-butylphenylboronic acid (2.2e.q.), repeat the above operation to obtain 348 mg of 3-1 yellow powder with a yield of 79%. 1 H NMR (300MHz, CDCl 3 )δ9.90(s, 1H), 8.01(t, 2H), 7.78(d, J=8.1Hz, 2H), 7.57(d, J=8.1Hz, 2H), 7.41(s, 1H), 7.24( s,1H),1.39(s,9H); 13 C NMR (75MHz, CDCl 3 )δ173.1,152.5,134.3,132.4,127.7,127.4,127.3,126.4,123.9,123.7,122.1,121.8,117.5,34.9,31.2.HRMS(ESI)calcd.for C 19 h 19 NO[M+H] + :278.1539,found278.1539.

[0060] In a 50 ml round bottom flask, add 20 ml of CH under argon 2 Cl 2 , add aldehyde (90 mg, 0.5 mmol), and add POCl which has been dissolved in 1 mL of dichloromethane 3 (0.47ml, 5mmol). After reacting for 4 hours, 1.0ml of diisopropylamine was added at room temperature, and after stirring at room temperature for 10 minutes, 1.2mL of boron trifluoride ether was added, and the round bottom flask was sealed. After stirring at room temperature for 2 h, extraction, drying, concent...

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Abstract

The invention relates to a near-infrared fluorine-boron dipyrrole fluorochrome and a preparation method thereof. According to the method, halogenated isoindole imine and a boric acid reagent Suzuki are coupled, and then the near-infrared fluorine-boron dipyrrole fluorochrome is synthesized through acid catalysis condensation, wherein the emission wavelengths of the fluorochrome in various solvents are greater than 669nm, and the emission spectrum of the fluorochrome and derivatives thereof can reach 748nm. The fluorochrome has relatively high fluorescence quantum yield (0.67-1) and excellent optical physicochemical properties, such as light stability, and has a good application prospect in fields like laser dye and bioanalysis.

Description

technical field [0001] The invention relates to the technical fields of functional fluorescent dyes, organic chemicals and fine chemicals, in particular to a near-infrared fluoroboron dipyrrole fluorescent dye and a preparation method thereof. Background technique [0002] Fluoroboron dipyrrole molecules are a class of fluorescent dye molecules with excellent photophysical and chemical properties that have only been developed in the past two decades. Chemical batteries, light-harvesting antenna systems and other fields have very good application prospects, and are widely used, especially the long-wave near-infrared fluoroboron dipyrrole molecule. Therefore, the synthesis of near-infrared fluoroborate dipyrrole fluorescent dyes has received greater attention. The approach of the near-infrared BODIPY fluorescent dye of synthesizing long-wave absorption emission usually has following several at present: 1) introduce aryl, vinyl, styryl, arylethynyl etc. [Rurack, K.; Kollmannsb...

Claims

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Application Information

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IPC IPC(8): C09B23/04C09K11/06
Inventor 郝二红徐雅俊于长江焦莉娟
Owner ANHUI NORMAL UNIV
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