Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate

A technology for nitrating monothiocyclic perylene tetracarboxylic acid and perylene tetracarboxylic acid, which can be used in organic chemistry and other directions, can solve complex problems, and achieve the effects of expanding conjugated system, mild reaction conditions, and enhancing molecular planarity

Inactive Publication Date: 2015-10-14
SHANDONG NORMAL UNIV
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  • Abstract
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Problems solved by technology

At present, the ring expansion reaction of perylene derivatives basically requires cyclization under light conditions or metal catalysis, and both methods are relatively complicated.

Method used

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  • Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate
  • Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate
  • Preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene tetracarboxylic n-butyl acrylate

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040] (1) Preparation of five-membered sulfur heterocyclic perylene tetracarboxylate n-butyl ester in bay position:

[0041] Add 40 mg (1.25 mmol) of sulfur powder and 8 ml of N-methylpyrrolidone (NMP) into a 25 ml round bottom flask, and stir at 90° C. for 10 minutes. Under argon protection, 50 mg (0.073 mmol) of n-butyl mononitrated perylene tetracarboxylate was added, reacted at 110°C for 6 hours, and followed the reaction by thin-layer chromatography. After the reaction, the reaction solution was poured into 100 ml of water to precipitate a precipitate, left to stand, and filtered under reduced pressure, the filter cake was washed 2 to 3 times with 10% ethanol aqueous solution, and the collected solid was vacuum-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography, and the eluent was dichloromethane:ethyl acetate=20:1. Obtained 35 mg (0.051 mmol, about 70% yield) of intermediate product.

[0042] (2) The preparation of mon...

Embodiment 2

[0049] (1) Preparation of five-membered sulfur heterocyclic perylene tetracarboxylate n-butyl ester in bay position:

[0050] Add 40 mg (1.25 mmol) of sulfur powder and 10 ml of N,N-dimethylformamide into a 25 ml round bottom flask, and stir at 90° C. for 10 minutes. Add 50 mg (0.073 mmol) n-butyl mononitrated perylenetetracarboxylate under nitrogen protection, react at 120° C. for 5 hours, follow the reaction by thin-layer chromatography. After the reaction, the reaction solution was poured into 100 ml of water to precipitate a precipitate, left to stand, and filtered under reduced pressure, the filter cake was washed 2 to 3 times with 10% ethanol aqueous solution, and the collected solid was vacuum-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography, and the eluent was dichloromethane:ethyl acetate=20:1. Obtained 35 mg (0.051 mmol, about 70% yield) of intermediate product.

[0051] (2) The preparation of mono-nitration and e...

Embodiment 3

[0057] (1) Preparation of five-membered sulfur heterocyclic perylene tetracarboxylate n-butyl ester in bay position:

[0058] Add 40 mg (1.25 mmol) of sulfur powder and 8 ml of dimethyl sulfoxide into a 25 ml round bottom flask, and stir at 90° C. for 10 minutes. Under argon protection, 50 mg (0.073 mmol) of n-butyl mononitrated perylene tetracarboxylate was added, reacted at 120°C for 4 hours, and followed the reaction by thin-layer chromatography. After the reaction, the reaction solution was poured into 100 ml of water to precipitate a precipitate, left to stand, and filtered under reduced pressure, the filter cake was washed 2 to 3 times with 10% ethanol aqueous solution, and the collected solid was vacuum-dried to obtain a crude product. The crude product was subjected to silica gel column chromatography, and the eluent was dichloromethane:ethyl acetate=20:1. Obtained 35 mg (0.051 mmol, about 70% yield) of intermediate product.

[0059] (2) The preparation of mono-nitra...

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Abstract

The present invention discloses a preparation method of bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene n-butyl tetracarboxylate. The method comprises the steps of: dissolving bay-bit mononitration-3,4:9,10-perylene n-butyl tetracarboxylate in N-methylpyrrolidone, reacting with elemental sulfur to obtain an intermediate product bay-bit embedded pentabasic sulfur heterocycle-3,4:9,10-perylene n-butyl tetracarboxylate; further nitrating the intermediate product to obtain the bay-bit mononitration single sulfur ring perylene n-butyl tetracarboxylate; and reacting the bay-bit mononitration single sulfur ring perylene n-butyl tetracarboxylate with an acid-binding agent and a nucleophilic reagent capable of forming carbanion to obtain the desired product bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene n-butyl tetracarboxylate. The bay-bit embedded pentabasic sulfur heterocycle and hexahydric oxygen heterocycle 3,4:9,10-perylene n-butyl tetracarboxylate prepared by the invention employs different annulations at two sides of the bay-bit, substantially enlarges the molecular conjugated system, enhances molecular flatness, and can select different substituents to change intramolecular charge distribution, so as to tune electronic structure and photophysical property of the molecule.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a preparation method of n-butyl perylene tetracarboxylate embedding five-membered sulfur heterocycles and six-membered oxygen heterocycles in the bay position. Background technique [0002] Perylene tetracarboxylic acid n-butyl ester derivatives are widely used in organic field effects due to their good electron-accepting ability, high fluorescence quantum yield, high photothermal stability, unique photoelectric properties and redox properties. Transistors, photochromic materials, light-absorbing arrays, organic solar cells, light-emitting diodes, and liquid crystal color filters are recognized as a class of organic dyes with extremely high utilization value. Therefore, it is particularly important to derivatize n-butyl perylene tetracarboxylates. Among them, the ring expansion reaction can increase the conjugated π system of perylene derivatives, thereby effectively ...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D495/06C07D495/10
CPCC07D495/06C07D495/10
Inventor 石志强赵云龙
Owner SHANDONG NORMAL UNIV
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