Dicyanomethylene-4H-pyran derivatives as well as preparation method and application thereof

A technology of dicyanomethylene and pyran derivatives, applied in chemical instruments and methods, luminescent materials, color-changing fluorescent materials, etc., can solve problems affecting the luminescent properties of organic molecules, fluorescence quenching, etc., and achieve good scientific research value and industrial application potential, easy purification, and simple synthesis process

Active Publication Date: 2017-11-24
WENZHOU UNIVERSITY
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

[0003] The dicyanomethylene-4H-pyran unit has a longer emission wavelength and a high fluorescence quantum yield due to the ultrafast intramolecular fast charge transfer effect in its structure, and is an ideal choice for the construction of red light materials. Excellent fluorophore, but so far, its derivatives are prone to fluorescence quenching due to the π-π stacking effect in the aggregated state, which limits their application as fluorescent materials in film-forming or solid-state forms (see literature: Chem.Commun., 2012,

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  • Dicyanomethylene-4H-pyran derivatives as well as preparation method and application thereof
  • Dicyanomethylene-4H-pyran derivatives as well as preparation method and application thereof
  • Dicyanomethylene-4H-pyran derivatives as well as preparation method and application thereof

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specific Embodiment 1

[0066] Dicyano methylene-4H-pyran derivative, its structural formula is as follows:

[0067]

[0068] The preparation method of dicyano methylene-4H-pyran derivative comprises the following steps:

[0069] (1) Using 2,6-dimethyl-4-pyrone 1 as a starting material, an addition-elimination reaction occurs with malononitrile to obtain intermediate 2;

[0070] (2) Addition-elimination reaction of intermediate 2 with indole aldehydes with different alkyl chains to obtain dicyanomethylene-4H-pyran derivatives.

[0071] Characterization of the dicyanomethylene-4H-pyran derivative 6a: 1 H NMR (DMSO-d 6 ,500MHz), δ(ppm):11.87(s,2H),8.25(d,J=8.0Hz,2H),8.04-7.98(m,4H),7.51(d,J=8.0Hz,2H),7.28 -7.19(m,6H),6.92(s,2H). 13 C NMR (DMSO-d 6 , 125MHz), δ (ppm): 160.3, 156.3, 137.6, 132.6, 132.5, 124.6, 122.7, 120.9, 120.8, 116.6, 113.3, 112.7, 112.4, 104.3, 52.6. MS(ESI,m / z):427.10(M + +H). Anal.calcd for C 28 h 18 N 4 O: C, 78.86; H, 4.25; N, 13.14. Found: C, 79.29; H, 4.22; N, 13....

specific Embodiment 2

[0087] Dicyano methylene-4H-pyran derivative, its structural formula is as follows:

[0088]

[0089] The preparation method of dicyano methylene-4H-pyran derivative comprises the following steps:

[0090] (1) Using 2,6-dimethyl-4-pyrone 1 as a starting material, an addition-elimination reaction occurs with malononitrile to obtain intermediate 2;

[0091] (2) Addition-elimination reaction of intermediate 2 with indole aldehydes with different alkyl chains to obtain dicyanomethylene-4H-pyran derivatives.

[0092] Characterization of the dicyanomethylene-4H-pyran derivative 6b: 1 H NMR (CDCl 3 ,500MHz), δ(ppm):7.94(d,J=7.5Hz,2H),7.72(d,J=15.5Hz,2H),7.51(s,2H),7.23(d,J=8.0Hz,2H ),7.36-7.30(m,4H),6.67(d,J=16.0Hz,2H),6.48(s,2H),4.19(t,J=7.0Hz,4H),1.91-1.87(m,4H) , 1.43-1.37 (m, 4H), 0.99 (t, J=7.0Hz, 6H). 13 C NMR (CDCl 3 ,125MHz), δ (ppm): 159.7, 156.2, 137.6, 132.1, 131.2, 125.9, 123.2, 121.6, 120.5, 116.5, 113.5, 112.9, 110.5, 104.8, 55.6, 46.7, 32.0, 20.2, 13.6. MS(ES...

specific Embodiment 3

[0113] Dicyano methylene-4H-pyran derivative, its structural formula is as follows:

[0114]

[0115] The preparation method of dicyano methylene-4H-pyran derivative comprises the following steps:

[0116] (1) Using 2,6-dimethyl-4-pyrone 1 as a starting material, an addition-elimination reaction occurs with malononitrile to obtain intermediate 2;

[0117] (2) Addition-elimination reaction of intermediate 2 with indole aldehydes with different alkyl chains to obtain dicyanomethylene-4H-pyran derivatives.

[0118] Characterization of the dicyanomethylene-4H-pyran derivative 6c: 1 H NMR (CDCl 3 ,500MHz), δ(ppm):7.96-7.94(m,2H),7.73(dd, 3 J=16.0Hz, 4 J=3.5Hz, 2H), 7.49(d, J=3.5Hz, 2H), 7.42(dd, 3 J=7.5Hz, 4 J=3.0Hz, 2H), 7.36-7.27(m, 4H), 6.69(dd, 3 J=16.0Hz, 4 J=3.5Hz, 2H), 6.49(d, J=3.5Hz, 2H), 3.39(dd, 3 J=7.0Hz, 4 J=3.5Hz, 4H), 2.29-2.24(m, 2H), 0.99(dd, 3 J=6.5Hz, 4 J=3.5Hz, 12H). 13 C NMR (CDCl 3 ,125MHz), δ (ppm): 159.7, 156.2, 137.8, 132.8, 131.3, 125.8, 1...

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Abstract

The invention particularly relates to dicyanomethylene-4H-pyran derivatives as well as a preparation method and an application thereof. The preparation method of the dicyanomethylene-4H-pyran derivatives comprises the following steps: (1) 2,6-dimethyl-4H-pyran-4-one 1 as a starting material is subjected to an addition-elimination reaction with malononitrile, and an intermediate 2 is obtained; (2) the intermediate 2 is subjected to an addition-elimination reaction with indolal with different alkyl chains, and the dicyanomethylene-4H-pyran derivatives are obtained. Indole structural units with different alkyl groups and dicyanomethylene-4H-pyran structural units are introduced into the field of organic solid luminescent materials, novel piezoluminescence color change materials are developed, and the derivatives play an important role in the field of photoelectricity. The provided method adopts a simple synthesis process, purification is easy, and the synthesized piezoluminescence materials are quite applicable to various fields of preparation of pressure sensors, anti-counterfeiting trademarks and the like and have good scientific research value and industrialized application potential.

Description

technical field [0001] The invention belongs to the field of organic synthesis and application, and specifically relates to dicyanomethylene-4H-pyran derivatives and their preparation methods and applications. Background technique [0002] Piezoluminescence of organic molecules is a class of "smart" materials. For the stimulation of external force, its solid-state fluorescent color can show obvious changes. And because of its potential applications in the fields of fluorescent sensors, data storage, security inks and optoelectronic devices, it has been valued by the scientific and industrial circles. (See literature: J. Am. Chem. Soc., 2005, 127, 11661-11665; Adv. Funct. Mater., 2007, 17, 3799-3807; Chem. Commun., 2013, 49, 273-275). [0003] The dicyanomethylene-4H-pyran unit has a longer emission wavelength and a high fluorescence quantum yield due to the ultrafast intramolecular fast charge transfer effect in its structure, and is an ideal choice for the construction of...

Claims

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Application Information

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IPC IPC(8): C07D405/14C09K11/06C09K9/02
CPCC07D405/14C09K9/02C09K11/06C09K2211/1029C09K2211/1088
Inventor 黄小波钱乐彬吴华悦周一斌刘妙昌高文霞丁金昌
Owner WENZHOU UNIVERSITY
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