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A kind of method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis

A technology for the preparation of benzazepine and catalysis, which is applied in the field of catalytic synthesis, can solve problems such as unfavorable reaction universality, operation, large-scale application of limiting schemes, harsh reaction conditions, etc., and achieve good yield, wide application range, and reaction The effect of system saving

Active Publication Date: 2022-07-08
SHANTOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] Since the construction of the aza seven-membered ring is relatively challenging, the reaction conditions of the above-mentioned technical scheme are relatively harsh, for example: by adding strong acid and some catalysts with high toxicity, it is not conducive to the universality and operation of the reaction; Adding an equivalent amount of alkali and heating to reflux for reaction, it is easy to generate some by-products; it is realized by electrochemistry, the operation is more complicated, and more expensive RVC electrodes are needed for anodic oxidation, and some electrolytes are needed in the reaction system Addition, and the need for an equivalent amount of alkali to participate in the reaction, is wasteful, not environmentally friendly, and often results in the generation of miscellaneous products
These shortcomings will limit the large-scale application of the above scheme

Method used

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  • A kind of method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis
  • A kind of method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis
  • A kind of method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0036] Dissolve 0.25 mmol of pyridine-N-oxide and 0.25 mmol of trifluoroacetic anhydride in 6 mL of dichloromethane to obtain a dichloromethane solution; use Ru(bpy) 3 Cl 2 ·6H 2 O( Tris(2,2'-bipyridyl)ruthenium chloride hexahydrate ) is a visible light catalyst, and 0.8 mg of this catalyst is added to a dichloromethane solution; 0.1 mmol of alkynylamine compound-1(R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 for H, R 10 for CF 3 CO) was added to the dichloromethane solution. The concentration of photosensitizer is 1.7×10 -4 M. Argon was used to deoxygenate for 10 min, and then irradiated with 450 nm±10 nm Blue LEDs for 9 h at room temperature under the stirring of a magnetic stirrer. After the reaction, the solvent was removed by distillation under reduced pressure, and the corresponding product was obtained by thin-layer chromatography. It was identified as aza-seven-membered ring benzazepine product-2(R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R...

Embodiment 2

[0038] Same as Example 1, the difference is: add 1.5mg visible light catalyst, the concentration of photosensitizer is 3.3×10 -4 M. The product is aza seven-membered ring benzazepine products-2(R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 for H, R 10 for CF 3 CO, R 11 for CF 3 ). The yield of product was 73%.

Embodiment 3

[0040] Same as Example 1, the difference is: add 2.3mg visible light catalyst, the concentration of photosensitizer is 5.0×10 -4 M. The product is aza seven-membered ring benzazepine products-2(R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 for H, R 10 for CF 3 CO, R 11 for CF 3 ). The yield of the product was 85%.

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Abstract

The invention relates to a method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis. 3 Cl 2 ·6H 2 O is added to the solvent to obtain a mixed solution, and the mixed solution is irradiated with visible light at room temperature under an inert gas atmosphere to obtain an aza seven-membered ring benzazepine compound. In the present invention, a simple, efficient and green method is used to construct aza seven-membered ring benzazepine compounds, and the reaction can occur by utilizing sunlight, which is very green; It is a high-grade reaction, and has a good yield, which reflects high efficiency; and the use of a catalytic amount of photosensitizer reflects the saving and environmental protection of the reaction. In addition, the method of the invention is convenient to operate, has mild reaction conditions, simple and easy-to-obtain raw materials, and the reaction can be efficiently realized by using a catalytic amount of photosensitizer, which has huge potential large-scale application value.

Description

technical field [0001] The invention belongs to the technical field of catalytic synthesis, in particular to a method for preparing aza seven-membered ring benzazepine compounds by visible light catalysis. Background technique [0002] Nitrogen-containing heterocyclic skeletons are widely found in biologically active natural products and drug molecules. Among them, aza-seven-membered ring skeleton compounds occupy a very important position (such as Metapramine, LXR ligand, Mianserin, etc.). Among such skeleton compounds, benzazepines have attracted extensive attention due to their excellent pharmacological activity. How to construct aza-seven-membered ring benzazepines is a hot research topic in the field of organic synthetic chemistry. one of the contents. However, the synthesis of aza seven-membered ring frameworks is very challenging due to its unique thermodynamic and kinetic characteristics. At present, there are some reports on the successful synthesis of aza seven-m...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D223/20
CPCC07D223/20Y02P20/584
Inventor 钟建基齐绪宽佟庆笑
Owner SHANTOU UNIV
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