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Application of HEH in catalyzing reaction of aryl halogen and aryl sulfinate to prepare sulfone compounds

A technology of aryl sulfinate and aryl halogen, which is applied in the field of catalytic chemistry, can solve the problems of high reduction potential and achieve high yield

Active Publication Date: 2020-04-28
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, using HEH as the catalyst and cesium carbonate as the base, a series of cross-coupling reactions between aryl halides and sulfinates were realized under blue LED irradiation, overcoming Solve the problem that the arylation reaction of arylating reagents and sulfinates in the prior art cannot be induced by visible light because of its high reduction potential

Method used

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  • Application of HEH in catalyzing reaction of aryl halogen and aryl sulfinate to prepare sulfone compounds
  • Application of HEH in catalyzing reaction of aryl halogen and aryl sulfinate to prepare sulfone compounds
  • Application of HEH in catalyzing reaction of aryl halogen and aryl sulfinate to prepare sulfone compounds

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Example 1: The HEH catalytic system catalyzes the reaction of 4-cyanohalobenzene and sodium benzenesulfinate.

[0028]

[0029] 4-cyanohalobenzene (X = Cl, Br, Cl, 0.2 mmol), sodium benzenesulfinate (0.4 mmol), Cs 2 CO 3 (0.3mmol), HEH (20 mol%, 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 (X = I, yield 95%; X = Br, yield 92%; X = Cl, yield 83%) was obtained.

[0030] 1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.05 (d, J = 7.9 Hz, 2H), 7.95 (d, J =7.7 Hz, 2H), 7.80 (d, J = 8.0 Hz,...

Embodiment 2

[0031] Example 2: The HEH catalytic system catalyzes the reaction of 4-acetylbromobenzene and sodium benzenesulfinate.

[0032]

[0033] 4-Acetylbromobenzene (0.2 mmol), sodium benzenesulfinate (0.4 mmol), Cs 2 CO 3 (0.3 mmol), HEH (20mol%) 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 (91% yield). Cs 2 CO 3 Replaced with potassium carbonate, the rest remained unchanged, to obtain the target product (yield 90%).

[0034] 1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.09–8.01 (m, 4H), 7.96 (d...

Embodiment 3

[0036] Embodiment 3: HEH catalytic system catalyzes the reaction of methyl 4-bromobenzoate and sodium benzene sulfinate.

[0037]

[0038] Methyl 4-bromobenzoate (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 (91% yield).

[0039] 1 H-NMR (400 MHz, CDCl 3 , ppm): δ 8.15 (d, J = 8.3 Hz, 2H), 8.02 (d, J =8.3 Hz, 2H), 7.96 (d, J = 7.6 Hz, 2H), 7.60 (t, J = 7.2 Hz, 1H), 7.53 (t, J =7.5 Hz, 2H), 3.9...

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Abstract

The invention discloses application of 2,6-dimethyl-1,4-dihydro-3,5-pyridine diethyl dicarboxylate as a visible light reduction catalyst to induce transition-metal-free catalysis of aryl halogen and aryl sulfinate so as to prepare sulfone compounds. The method comprises the following steps: under inert gas protection, adding the reactants into a reaction container provided with a stirring device according to the molar ratio of aryl halogen compounds, sulfinate compounds, inorganic alkali to HEH being 1:2:1.5:0.2, then adding dimethyl sulfoxide, and carrying out stirring reaction for 24 hours at room temperature under blue LED irradiation to obtain the sulfone compounds. According to the method, the HEH is used as a catalyst for the first time under the condition that no auxiliary transition metal catalyst is added, and a series of cross-coupling reactions of aryl halogen and sulfinate are realized. In addition, the whole process is green, efficient and easy to operate, and the method is a good method for synthesizing sulfone 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) as a visible light reduction catalyst to induce transition metal-free catalyzed aryl Application of halogen and aryl sulfinate to prepare sulfone compounds. Background technique [0002] 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, at higher temperatures, the cross-coupling reaction of aryl halides and sulfinates is catalyzed by palladium or copper; some research groups use ruthenium or iridium noble metal complexes as photosensitizers, and then combine them with nickel catalysts, The cross-coupling reaction of aryl halide and sulfinate was realized. However, these methods require the combination of expe...

Claims

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Application Information

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IPC IPC(8): B01J31/02C07B45/04C07C315/00C07C317/24C07C317/14C07C317/22C07C317/44
CPCB01J31/0244C07B45/04C07C315/00B01J2231/4294C07C317/44C07C317/24C07C317/14C07C317/22
Inventor 李红喜朱大亮钟胜奎李海燕
Owner SUZHOU UNIV
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