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Nitrogen-containing cation chromophore and preparation thereof

A technology of cationic and nitrogen elements, applied in the direction of luminescent materials, acridine dyes, organic dyes, etc., can solve the problems of poor solubility, catalyst deactivation, unstable reaction system, etc., to prevent accumulation effect, improve stability, and save time long effect

Inactive Publication Date: 2014-08-13
CHONGQING TECH & BUSINESS UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] When rhodamine derivatives with S and Se elements as bridge atoms are used as photosensitizers, they have the advantages of longer absorption and excitation wavelengths, higher excited triplet quantum yields, and easy solubility in water. However, they are easy to coordinate with metal catalysts. Shortcomings such as the formation of complexes and the short duration of excited triplet states lead to unstable reaction systems, catalysts are prone to deactivation, and hydrogen production lasts for a short time (J.Phys.Chem.B, 2004, 108, 8668-8672; J.Am .Chem.Soc.2010, 132, 15480-15483)
Studies have shown that the 9-trimethylphenyl-10-methylacridinium ion using nitrogen as a bridge atom has a similar parent ring structure to rhodamine, and has the advantages of stable properties and a long existence time of the excited triplet state. There are disadvantages such as poor solubility in aqueous solution, short absorption and excitation and emission wavelengths, which limit its application as a photosensitizer (J.Am.Chem.Soc.2012, 134, 4569-4572)

Method used

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  • Nitrogen-containing cation chromophore and preparation thereof
  • Nitrogen-containing cation chromophore and preparation thereof
  • Nitrogen-containing cation chromophore and preparation thereof

Examples

Experimental program
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Effect test

example 1

[0035]

[0036] Step ①: Put 0.04 mol of N,N-dimethyl-m-bromoaniline, 21.6mL of 30% methylamine aqueous solution (containing about 0.10 mol of methylamine), and 0.002 mol of copper powder into a 50mL sealed tube, and react at 100°C for 12h Afterwards, cool to room temperature, extract 3 times with 40 mL of ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate, recrystallize in ethanol for separation and purification, and obtain 5.64 g of the reaction product of step ①;

[0037] The second step: 0.024 moles of the first step product, 0.020 moles of N,N-dimethyl-iodoaniline and 0.024 moles of KN(Si(CH 3 ) 3 ) 2 Dissolve in 50 mL of dioxane, under nitrogen protection, react at 100°C for 30 minutes, add 15 mL of water to quench the reaction, cool to room temperature, extract 3 times with 30 mL of ethyl acetate / tetrahydrofuran with a molar ratio of 1:1, and combine The organic phase was saturated with Na 2 CO 3 The solution was wash...

example 2

[0040]

[0041] Step ①: Put 0.02 mol of N,N-dimethyl-m-bromoaniline, 0.04 mol of benzylamine, and 0.01 mol of copper powder into a 25mL sealed tube, react at 100°C for 12h, cool to room temperature, and wash with 30mL ethyl acetate The ester was extracted 3 times, the organic phases were combined, dried with anhydrous sodium sulfate, filtered, concentrated, separated and purified by recrystallization in ethanol to obtain 4.10 g of the reaction product of step ①;

[0042] The ② step: 0.018 moles of the ① step product, 0.015 moles of N, N-dimethyl iodoaniline and 0.018 moles of KN(Si(CH 3 ) 3 ) 2 Dissolve in 30mL of dioxane, under the protection of nitrogen, react at 100°C for 30 minutes, add 10mL of water to quench the reaction, cool to room temperature, extract 3 times with 20mL of ethyl acetate / tetrahydrofuran with a molar ratio of 1:1, and combine The organic phase was saturated with Na 2 CO 3 The solution was washed, dried over anhydrous sodium sulfate, filtered, con...

example 3

[0045]

[0046] Step ①: put 1.6 moles of N, N-dimethyl-m-bromoaniline, 800 mL of 30% methylamine aqueous solution (containing about 4 moles of methylamine), and 0.08 moles of copper powder into a 1.5 L sealed tube, and react at 100 ° C for 18 hours Afterwards, cool to room temperature, extract 3 times with 300 mL ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, filter, concentrate, separate and purify by recrystallization in ethanol, and obtain 226.30 g of the reaction product of step ①;

[0047] Step ②: 1.2 moles of the product of step ①, 1 mole of N,N-dimethyl-iodoaniline and 1.2 moles of KN(Si(CH 3 ) 3 ) 2 Dissolve in 1.5L of dioxane, react at 100°C for 50 minutes under nitrogen protection, add 2.5L of water to quench the reaction, cool to room temperature, and extract 3 times with 120mL of ethyl acetate / tetrahydrofuran with a molar ratio of 1:1 , combine the organic phases and wash with saturated Na 2 CO 3 The solution was washed, dried ...

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Abstract

To solve the problems caused by using rhodamine derivatives and 9-trimethylbenzyl-10-methylacridine ion that take S and Se as the bridge atoms as the photosensitive agents, the invention provides a novel nitrogen-containing cation chromophore and a preparation method thereof. The compound has the characteristics of long absorption wavelength, long excitation wavelength, high quantum yield and long exiting time of excited triplet state generated by absorbing photons, easy water-solubility, and incapability of coordinating with metal catalysts. The preparation method comprises the following steps: making m-bromoaniline derivatives carry out Ullmann C-N coupling reactions with excess primary amine in the presence of a CuI catalyst so as to obtain a reaction product A; making the reaction product A carry out Ullmann C-N coupling reactions with m-iodoaniline derivatives in the presence of KN(Si(CH3)3)2 so as to obtain a reaction product B; making the reaction product B carry out Bayer condensation reactions with benzaldehyde derivatives in the present of a ferric trichloride catalyst or a zinc dichloride catalyst to enclose the ring so as to obtain a reaction product C; and finally carrying out a dehydration treatment on the reaction product C with 2,3-dicyano-5,6-dichlorobenzoquinone (DDQ) so as to obtain the target product.

Description

technical field [0001] The invention relates to a novel nitrogen-containing cationic chromophore and a preparation method thereof. Background technique [0002] Cationic fluorescent chromophores have superior spectral properties and are widely used dyes and fluorescent luminescent agents in industry. Rhodamine and its derivatives are the earliest cationic fluorescent chromophores, which belong to xanthene compounds, because of their relatively long excitation and emission wavelengths, high quantum yield, good water solubility and high stability. properties, are widely used in fluorescent labeling reagents and dye laser light sources. There are many structural modifications based on rhodamine, and new patents are published continuously, such as US patents US6130101 and US6162610 in 2000, and Chinese patent CN100361999 in 2008. These studies show that replacing the oxygen bridge atoms in rhodamine with other bridge atoms has a great influence on the fluorescence properties o...

Claims

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Application Information

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IPC IPC(8): C09K11/06C09B15/00C07D219/08
CPCC09B15/00C09K11/06
Inventor 蒋彦可朱秀
Owner CHONGQING TECH & BUSINESS UNIV
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