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Method for preparing beta-carbonyl sulfone

A carbonyl sulfone and carbonyl technology, applied in the field of preparation of β-carbonyl sulfone, can solve the problems of cumbersome reaction steps, cumbersome reaction operation, narrow substrate range, etc., and achieves good substrate universality, simple reaction operation and atom economy. Good results

Active Publication Date: 2020-02-21
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] (2) Knospe, R.H. et al. reported the synthesis of β-carbonyl sulfone compounds using the Claisen condensation reaction strategy, but the disadvantage of the reaction is that it needs to use a strong base sodium ethoxide, which is not friendly to the environment, and the reaction steps are cumbersome and the substrate range Also relatively narrow (cf. Knospe, R.H. J. Am. Chem. Soc . 1955, 77 , 5063);
The disadvantage of the reaction is that the atom economy of the reaction is relatively poor, the reaction conditions are relatively harsh, and the price of PhI(OH)OTs is relatively expensive
[0006] In summary, the currently reported methods for the synthesis of β-carbonyl sulfones have obvious disadvantages, such as: high cost, cumbersome reaction operations, harsh reaction conditions, poor atom economy, narrow substrate range, etc.

Method used

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  • Method for preparing beta-carbonyl sulfone
  • Method for preparing beta-carbonyl sulfone
  • Method for preparing beta-carbonyl sulfone

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0035]

[0036] Add AgNO once in the test tube 3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K 2 S 2 o 8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2a (1.0 mmol, 114.1 mg), MeCN / H 2 O = 10:1 (2.0 mL). Then the system was heated and stirred at 70°C in air for 4 hours, the reaction system was quenched with saturated sodium sulfite solution, extracted with ethyl acetate three times, and the organic layers were combined and dried with anhydrous sodium sulfate. Then remove the solvent, absorb on silica gel and pass column chromatography to get the product β-carbonyl sulfone 3aa with a yield of 80%. When the reaction was scaled up to 10 mmol (compound 1a), the target product 3aa was still obtained in 74% yield. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0037] 1 H NMR (400 MHz, CDCl 3 ) δ 7.97-7.95 (m, 2H), 7.72-7.68 (m, 1H), 7.6...

Embodiment 2

[0039]

[0040] Add AgNO once in the test tube 3(0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K 2 S 2 o 8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2b (1.0 mmol, 128.1 mg), MeCN / H 2 O = 10:1 (2.0 mL). Then the system was heated and stirred at 70°C in air for 4 hours, the reaction system was quenched with saturated sodium sulfite solution, extracted with ethyl acetate three times, and the organic layers were combined and dried with anhydrous sodium sulfate. Then the solvent was removed, silica gel was adsorbed, and the product β-carbonyl sulfone 3ab was obtained by column chromatography with a yield of 76%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0041] 1 H NMR (400 MHz, CDCl 3 ) δ 7.97-7.94 (m, 2H), 7.71-7.67 (m, 1H), 7.60-7.57 (m, 2H), 4.99-4.93 (m, 1H), 4.12 (s, 2H), 1.15 (d, J = 6.3 Hz, 6H). 13 CNMR (100 MHz, CDCl 3 ...

Embodiment 3

[0043]

[0044] Add AgNO once in the test tube 3 (0.05 mmol, 8.5 mg), 1,10-phen (0.05 mmol, 9.0 mg), K 2 S 2 o 8 (0.25 mmol, 67.6 mg), 1a (0.5 mmol, 82.1 mg), 2c (1.0 mmol, 142.2 mg), MeCN / H 2 O = 10:1 (2.0 mL). Then the system was heated and stirred at 70°C in air for 4 hours, the reaction system was quenched with saturated sodium sulfite solution, extracted with ethyl acetate three times, and the organic layers were combined and dried with anhydrous sodium sulfate. Then the solvent was removed, silica gel was adsorbed, and the product β-carbonyl sulfone 3ac was obtained by column chromatography with a yield of 70%. The main test data of the obtained product are as follows. It can be seen from the analysis that the actual synthesized product is consistent with the theoretical analysis.

[0045] 1 H NMR (400 MHz, CDCl 3 ) δ 7.96-7.94 (m, 2H), 7.71-7.67 (m, 1H), 7.60-7.56 (m, 2H), 4.15 (s, 2H), 4.07 (t, J = 6.7 Hz, 2H), 1.55-1.48 (m, 2H),1.31-1.22 (m, 2H), 0.87 (t...

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Abstract

The invention discloses a method for preparing beta-carbonyl sulfone. The preparation method comprises the following steps: by taking an alpha-carbonyl diazo compound and sodium arylsulfinate as reaction substrates, cheap silver nitrate as an optimal catalyst, 1, 10-phenanthroline as a ligand and potassium persulfate as an oxidant, carrying out coupling reaction in a mixed solvent of acetonitrileand water to obtain the beta-carbonyl sulfone compound. Compared with the prior art, the method has the advantages of wide reaction substrate range, short reaction time, high reaction yield, mild reaction conditions and the like. Non-toxic and harmless reagents are used as reaction raw materials, so that the method is harmless to the environment and meets the requirements of modern green chemicaldevelopment. Post-reaction treatment is simple, and separation and purification are facilitated. In addition, the reaction can realize gram-scale synthesis, and lays a foundation for practical application.

Description

technical field [0001] The invention relates to a method for preparing β-carbonyl sulfone, which belongs to the technical field of organic synthesis. Background technique [0002] Sulfone-based skeleton compounds are widely used. In organic synthetic chemistry, sulfone-based compounds are also an important class of reaction intermediates. For example, through Julia alkenylation, Ramberg–Bäcklund reaction and Smiles rearrangement can be converted into corresponding target molecules. Due to their wide range of applications, they have received extensive attention from chemists in the past few decades, for which a series of methods for the synthesis of sulfone-based compounds have been developed. Among the numerous sulfone-based compounds, β-carbonyl sulfone compounds have received special attention. This type of compound has a wide range of activities and is often used for the total synthesis of natural products and the synthesis of heterocyclic compounds. Therefore, it is of ...

Claims

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Application Information

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IPC IPC(8): C07C315/00C07D333/16C07J1/00C07C317/44C07B45/04
CPCC07C315/00C07D333/16C07J1/0011C07B45/04C07C2601/14C07C317/44C07J31/006C07J41/0038C07C315/02C07C315/06C07C2523/50
Inventor 万小兵王航航郑永高廉鹏程李晶晶
Owner SUZHOU UNIV
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