Unlock instant, AI-driven research and patent intelligence for your innovation.

A light-induced metal-free catalyzed carboarylation tandem reaction for the synthesis of heterocyclic compounds

A technology of metal-free catalysis and heterocyclic compounds, applied in the direction of organic chemistry, can solve the problems of poor chemoselectivity, many by-products, and low yield, and achieve good chemoselectivity, good regioselectivity, and low energy consumption. Effect

Active Publication Date: 2021-07-30
HENAN UNIVERSITY
View PDF3 Cites 0 Cited by
  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In recent years, the reported methods of isoquinolinone and its derivatives often have harsh reaction conditions, low yields, many by-products, difficult purification, and expensive catalysts must be used in some methods
[0005] The preparation methods of the above two heterocyclic compounds still need Cu catalyst, the reaction temperature is higher, and the chemoselectivity of each reaction is poor, and only one product can be synthesized

Method used

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
View more

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1 4-acetyl-3-methylisoquinolin-1(2H)-one

[0027] O-bromobenzamide (0.5mmol, 100mg) (X=Br in formula III, R 1 =R 2 =H), acetylacetone (1.5mmol, 154µL) (R in formula IV 3 =R 4 =CH 3 , R 5 = H), Cs 2 CO 3 (1mmol, 326mg), eosin Y (0.025mmol, 17.3mg), DMSO (2.5mL) were added to a quartz reaction tube, and the mixture was stirred for 36 hours under nitrogen atmosphere and 254nm ultraviolet light at room temperature, and the reaction was monitored by TLC . After the reaction was complete, the reaction was cooled to room temperature, quenched with water, and extracted with ethyl acetate (3×10 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate=2:1) ​​to obtain 90 mg of a white solid product with a yield of 90%.

[0028] The NMR characterization of 4-acetyl-3-methylisoquinolin-1(2H)-one is as follows...

Embodiment 2

[0029] Example 2 4-acetyl-3-methyl-7-nitroisoquinolin-1(2H)-one

[0030] 5-Nitro-o-bromobenzamide (0.5mmol, 122.5mg) (X=Br in formula III, R 1 =NO 2 , R 2 =H), acetylacetone (1.5mmol, 154µL) (R in formula IV 3 =R 4 =CH 3 , R 5 = H), Cs 2 CO 3(1mmol, 326mg), Eosin B (0.025mmol, 15.6mg), DMF (2.5mL) were added to a quartz reaction tube, and the mixture was stirred for 36 hours under nitrogen atmosphere and 254nm ultraviolet light at room temperature, and the reaction was monitored by TLC . After the reaction was complete, the reaction was cooled to room temperature, quenched with water, and extracted with ethyl acetate (3×10 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate=2:1) ​​to obtain 117 mg of a yellow solid product with a yield of 95%.

[0031] The NMR characterization of 4-acetyl-3-methyl-7-nitroi...

Embodiment 3

[0032] Example 3 4-acetyl-3-cyclopropylisoquinolin-1(2H)-one

[0033] O-bromobenzamide (0.5mmol, 100mg) (X=Br in formula III, R 1 =R 2 =H), 1-cyclopropyl-1,3-butanedione (1.5mmol, 172µL) (R in Formula IV 3 =CH 3 , R 4 = Cyclopropyl, R 5 =H), t -BuOLi (1 mmol, 80.1 mg), I 2 (0.1mmol, 25.4mg), toluene (2.5mL) was added to a quartz reaction tube, and the mixture was stirred for 36 hours under a nitrogen atmosphere and irradiated by a xenon lamp at room temperature, and the reaction was monitored by TLC. After the reaction was complete, the reaction was cooled to room temperature, quenched with water, and extracted with ethyl acetate (3×10 mL). The combined organic extracts were washed with brine, dried over sodium sulfate, filtered, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether / ethyl acetate=2:1) ​​to obtain 89 mg of white solid product with a yield of 78%.

[0034] The NMR characterization of 4-acetyl-3-cyclopro...

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

PUM

No PUM Login to View More

Abstract

The invention belongs to the technical field of organic synthesis, and discloses a method for synthesizing heterocyclic compounds by light-induced metal-free catalyzed carbon arylation series reaction, comprising the following steps: using a compound shown in formula III and a compound shown in formula IV as The substrate, in an organic solvent, under the action of a photosensitizer and a basic compound, under the condition of room temperature illumination, stirred for 24-48 hours, quenched the reaction, extracted, washed, dried, concentrated, and purified to obtain formula I or formula II. Heterocyclic compounds shown. Compared with the traditional Ullmann-Hurtley coupling ring-closing reaction, the invention reacts under room temperature illumination without metal catalysis, does not need to add a catalyst, only needs to react at room temperature, has low energy consumption, and greatly reduces the occurrence of side reactions. ,Green.

Description

technical field [0001] The invention belongs to the technical field of organic synthesis, and relates to a method for synthesizing heterocyclic compounds by light-induced metal-free catalyzed carboarylation tandem reactions, in particular to photo-induced metal-free catalyzed carboarylation tandem reactions for synthesizing isoquinolinone compounds and The method of isocoumarins. Background technique [0002] The Ullmann reaction is a cross-coupling reaction under the condition of copper catalysis. Compared with many coupling reactions catalyzed by transition metals, the Ullmann reaction has advantages in terms of economy and environmental protection due to the use of copper reagents with low price and bottom poison. Great advantage. The researchers found that the Ullmann reaction can not only be applied to the formation of C-C, C-N, and C-O bonds, but also can be extended to the formation of C-S, C-P, and C-Se bonds, thereby broadening the scope of application of the Ullma...

Claims

the structure of the environmentally friendly knitted fabric provided by the present invention; figure 2 Flow chart of the yarn wrapping machine for environmentally friendly knitted fabrics and storage devices; image 3 Is the parameter map of the yarn covering machine
Login to View More

Application Information

Patent Timeline
no application Login to View More
Patent Type & Authority Patents(China)
IPC IPC(8): C07D217/24C07D471/04C07D311/76
CPCC07D217/24C07D311/76C07D471/04
Inventor 徐浩赖贞贞王延鹏许静任艳蓉刘保英张文凯徐元清房晓敏丁涛
Owner HENAN UNIVERSITY