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Method for preparing heterocyclic sulfone organic compounds

A technology of organic compounds and sulfones, applied in the field of catalytic chemistry, can solve problems such as high reduction potential of aryl halogens, and achieve the effect of high yield

Active Publication Date: 2021-08-27
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

That is, without adding any auxiliary transition metal catalyst, a series of heterocyclic aryl halogens were realized under the irradiation of blue LED (10 W, wavelength 460-485nm) with HEH as the catalyst and cesium carbonate as the base. The cross-coupling reaction with phenyl sulfinate overcomes the arylation reaction between arylating reagent and sulfinate in the prior art, which cannot be induced by visible light because aryl halogen has a high reduction potential question

Method used

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  • Method for preparing heterocyclic sulfone organic compounds
  • Method for preparing heterocyclic sulfone organic compounds
  • Method for preparing heterocyclic sulfone organic compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] Example 1: The HEH catalytic system catalyzes the reaction of 4-iodopyridine and sodium benzenesulfinate.

[0024]

[0025] 4-iodopyridine (0.2 mmol), sodium benzenesulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20mol%, 0.04 mmol) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted for 24 h under the irradiation of blue LED. After the reaction, 5 mL of water was added, then extracted with 3×5 mL of ethyl acetate, the organic phases were combined, and the organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. The target product was obtained (68% yield). will be replaced by K 2 CO 3 , and the rest remained unchanged, the target product was obtained (yield 62%).

[0026] 1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.80 (s, 2H), 7.95 (d, J = 7.1 H...

Embodiment 2

[0028] Example 2: The HEH catalytic system catalyzes the reaction of 4-bromo-2-trifluoromethylpyridine and sodium benzenesulfinate.

[0029]

[0030] 4-Bromo-2-trifluoromethylpyridine (0.2 mmol), sodium benzenesulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted for 24 h under the irradiation of blue LED. After the reaction, 5 mL of water was added, then extracted with 3×5 mL of ethyl acetate, the organic phases were combined, and the organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. The target product was obtained (yield 85%).

[0031] 1 H NMR (400 MHz, CDCl 3 , ppm): δ = 8.94 (d, J = 4.9 Hz, 1H), 8.13 (s,1H), 7.98 (t, J = 7.3 Hz, 3H), 7.69 (t, J = 7.4 Hz, 1H), 7.60 (t, J = 7.6 ...

Embodiment 3

[0033] Example 3: The HEH catalytic system catalyzes the reaction of 2-bromo-6-trifluoromethylpyridine and sodium benzenesulfinate.

[0034]

[0035] 2-Bromo-6-trifluoromethylpyridine (0.2 mmol), sodium benzenesulfinate (0.4 mmol), Cs 2 CO 3(0.3 mmol), HEH (20 mol%) and DMSO (1 mL) were added to a dry reaction tube with a magnetic stirrer, and then the reaction tube was washed with N 2 Replaced 3 times, stirred and reacted for 24 h under the irradiation of blue LED. After the reaction, 5 mL of water was added, then extracted with 3×5 mL of ethyl acetate, the organic phases were combined, and the organic phase was dried with anhydrous sodium sulfate, filtered, and the filtrate was concentrated by rotary evaporation and separated by silica gel column chromatography. The target product was obtained (yield 81%).

[0036] 1 H NMR (400 MHz, CDCl 3 , ppm): δ = 8.38 (d, J = 7.9 Hz, 1H), 8.12 (dd, J = 14.1, 7.6 Hz, 3H), 7.82 (d, J = 7.8 Hz, 1H), 7.65 (t, J = 7.3 Hz, 1H), ...

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Abstract

The invention discloses a method for preparing a heterocyclic sulfone organic compound from a heterocyclic aryl halogen and an aryl sulfinate. The method comprises the following steps: under the protection of an inert gas, according to the heterocyclic aryl halogen compound: benzenesulfin Acid salt compound: Inorganic base: The molar ratio between HEH is 1:2:1.5:0.2. Add the above reactants into the reaction vessel equipped with a stirring device, then add dimethyl sulfoxide, and irradiate with blue LED. The reaction was stirred at room temperature for 24 hours to obtain a heterocyclic sulfone organic compound. For the first time, the present invention realizes a series of cross-coupling reactions between heterocyclic aryl halogens and benzenesulfinate by using HEH as a catalyst without adding any auxiliary transition metal catalyst and noble metal photosensitizer. In addition, the whole process of the invention is green, efficient and easy to operate, and is a good method for synthesizing heterocyclic sulfone organic compounds.

Description

technical field [0001] The invention belongs to the technical field of catalytic chemistry, in particular to diethyl 2,6-dimethyl-1,4-dihydro-3,5-pyridinedicarboxylate (HEH) used as a visible light reduction catalyst to induce transition metal-free catalytic heterocycles A method for preparing heterocyclic sulfone organic compounds from aryl halides and aryl sulfinates. Background technique [0002] Organic sulfone compounds are not only an important class of organic complexes, but also widely exist in natural products, biologically active substances and drug molecules. To synthesize such compounds, various methods have been developed. For example, palladium or copper catalyzed cross-coupling reactions of heterocyclic aryl halides and sulfinates at higher temperatures; or oxidation of thioethers with excess inorganic oxidants to obtain such compounds, but this method has poor selectivity , easily produce by-products such as sulfoxide, and also produce a large amount of was...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07D213/71C07D213/84C07D215/36C07D333/34
CPCC07D213/71C07D213/84C07D215/36C07D333/34
Inventor 钟胜奎朱大亮李海燕李红喜
Owner SUZHOU UNIV
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