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Synthesis method of alpha, alpha-difluoro-beta-carbonyl sulfone compound

A synthetic method and compound technology, applied in the preparation of organic compounds, chemical instruments and methods, organic chemistry, etc., can solve problems that limit further applications

Active Publication Date: 2020-06-12
TAIZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[C.Ni, L.Zhang, J.Hu, J.Org.Chem.2009,74,3767] This method needs to be carried out under strong base LHMDS and ultra-low temperature (-98℃), which limits its further application

Method used

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  • Synthesis method of alpha, alpha-difluoro-beta-carbonyl sulfone compound
  • Synthesis method of alpha, alpha-difluoro-beta-carbonyl sulfone compound
  • Synthesis method of alpha, alpha-difluoro-beta-carbonyl sulfone compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027]

[0028] At room temperature, add p-tolyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), 2,2-difluoroenolsilyl ether (0.2mmol) and Ru(bpy) sequentially to a dry reaction tube 3 Cl 2 ·6H 2 O (0.004mmol), plugged the reaction tube with a stopper and replaced it in high-purity nitrogen for three times, so that the system was under anaerobic conditions, then added acetonitrile (2mL), and stirred under 15W blue light until the reaction was completely monitored by TLC. The reaction solution was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography to obtain the corresponding α,α-difluoro-β-carbonyl sulfone compound example 1.

[0029] Structural characterization of compound example 1: 1 H NMR (400MHz, CDCl 3)δ8.18(d, J=7.8Hz, 1H), 7.90(d, J=7.7Hz, 1H), 7.70(t, J=7.4Hz, 1H), 7.54(t, J=7.5Hz, 1H) ,7.44(d,J=7.8Hz,1H),2.50(s,2H). 13 C NMR (100MHz, CDCl 3 )δ1...

Embodiment 2

[0031]

[0032] Add phenyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), 2,2-difluoroenol silyl ether (0.2mmol) and Ru(bpy) sequentially to a dry reaction tube at room temperature 3 Cl 2 ·6H 2 O (0.004mmol), plugged the reaction tube with a stopper and replaced it in high-purity nitrogen for three times, so that the system was under anaerobic conditions, then added acetonitrile (2mL), and stirred under 15W blue light until the reaction was completely monitored by TLC. The reaction solution was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography to obtain the corresponding α,α-difluoro-β-carbonyl sulfone compound Example 2.

[0033] Structural characterization of compound example 2: 1 H NMR (400MHz, CDCl 3 )δ8.18(d, J=7.6Hz, 1H), 8.04(d, J=7.6Hz, 1H), 7.82(t, J=7.4Hz, 1H), 7.74-7.63(m, 2H), 7.55( t,J=7.5Hz,1H). 13 C NMR (100MHz, CDCl 3 )δ183.7(t, J=23.2...

Embodiment 3

[0035]

[0036] At room temperature, add p-chlorophenyldiazonium salt (0.3mmol), sodium metabisulfite (0.4mmol), 2,2-difluoroenol silyl ether (0.2mmol) and Ru(bpy) sequentially to the dry reaction tube 3 Cl 2 ·6H 2 O (0.004mmol), plugged the reaction tube with a stopper and replaced it in high-purity nitrogen for three times, so that the system was under anaerobic conditions, then added acetonitrile (2mL), and stirred under 15W blue light until the reaction was completely monitored by TLC. The reaction liquid was directly concentrated under reduced pressure, and the mixed system of petroleum ether and ethyl acetate was used as the mobile phase for column chromatography to obtain the corresponding α,α-difluoro-β-carbonyl sulfone compound example 3.

[0037] Structural characterization of compound example 3: 1 H NMR (400MHz, CDCl 3 )δ8.17(d, J=7.8Hz, 1H), 7.97(d, J=8.0Hz, 1H), 7.72(t, J=7.4Hz, 1H), 7.64(d, J=7.9Hz, 1H) ,7.56(t,J=7.6Hz,1H). 13 CNMR (100MHz, CDCl 3 )δ183....

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Abstract

The invention belongs to the technical field of organic chemistry, and particularly relates to a synthesis method of an alpha, alpha-difluoro-beta-carbonyl sulfone compound. The method comprises the following steps: with acetonitrile as a solvent, carrying out a reaction on aryl diazonium salt, sodium metabisulfite and 2,2-difluoroenol silyl ether with Ru(bpy)3Cl2.6H2O being a photosensitizer under blue light irradiation to obtain the 2, 2-difluoroenol silyl ether photosensitizer, thereby generating aryl sulfonyl free radicals from aryl diazonium salt and sodium pyrosulfite under the action of blue light and a photosensitizer, performing addition reaction on 2,2-difluoroenol silyl ether to obtain a free radical intermediate, and performing single-electron oxidation on the free radical intermediate and an excited photosensitizer to obtain the alpha, alpha-difluoro-beta-carbonyl sulfone compound. The synthesis method of the compound has the advantages that with the aryl diazonium salt,sodium metabisulfite and 2,2-difluoroenol silyl ether, which are easy to obtain, being raw materials, strict reaction conditions such as strong base and ultralow temperature are not needed, so that the method has the advantages of strong functional group compatibility, wide substrate application range and the like, a series of alpha, alpha-difluoro-beta-carbonyl sulfone compounds can be efficiently synthesized, and the method has good academic guidance significance and industrial application value.

Description

technical field [0001] The invention belongs to the technical field of organic chemistry, in particular to a method for synthesizing α,α-difluoro-β-carbonyl sulfone compounds Background technique [0002] α,α-Difluoro-β-carbonyl sulfone is a common sulfonyl compound containing a difluoromethyl structure. In the field of organic synthesis, α,α-difluoro-β-carbonyl sulfone compounds can be used as key intermediates to participate in nucleophilic addition, cycloaddition and free radical reactions to construct fluorine-containing compounds with important biological activities. [C.Ni, L. Zhang, J. Hu, J. Org. Chem. 2009, 74, 3767; (b) W. Ye, L. Zhang, C. Ni, J. Rong, J. Hu, Chem. Commun.,2014,50,10596.] In medicinal chemistry, the use of difluoromethyl groups as structural mimics of hydroxyl groups in bioactive molecules has also attracted widespread attention, and the introduction of difluoromethyl groups into bioactive molecules can significantly improve their Biometabolic sta...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C315/00C07C317/24
CPCC07C315/00C07C317/24
Inventor 何福生吴劼叶盛青
Owner TAIZHOU UNIV
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