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A method for electrochemically synthesizing α-acyloxy ketones

An acyloxyketone, electrochemical technology, applied in the field of electrochemical synthesis of α-acyloxyketone, can solve the problems of unfavorable industrial operation and large-scale production, limited application space, waste of resources and the environment, and achieves short preparation cycle, Strong process stability and the effect of reducing waste of resources

Inactive Publication Date: 2019-04-16
NANYANG NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0003] However, looking at the above-mentioned synthetic methods of α-acyloxyketone compounds that have been reported, the efficiency is often low, the reaction time is long, and it is not conducive to industrial operation and large-scale production, which greatly limits its application in the fields of organic synthesis and medicinal chemistry. space; at the same time, a large amount of oxidant is usually added during the synthesis process, which not only has certain safety hazards, but also causes waste of resources and environmental pollution due to excessive oxidant

Method used

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  • A method for electrochemically synthesizing α-acyloxy ketones
  • A method for electrochemically synthesizing α-acyloxy ketones
  • A method for electrochemically synthesizing α-acyloxy ketones

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0053] Add 10 g of raw material 4-benzoylbutyric acid, 2.8 g of catalyst tetra-n-butylammonium iodide, 12 g of electrolyte tetrabutylammonium acetate, 50 mL of acetonitrile, and 2 mL of trifluoroethanol into the electrolyzer without a diaphragm, respectively. Solvent, and then insert the graphite electrode, pass the current density of 10 mA / cm 2 constant current at 40 o The reaction was stirred under C; the reaction was tracked by thin layer chromatography, and after the completion of the reaction, the solvent was spun off under vacuum, and then isolated to obtain the product 5-benzoyl dihydrofuran-2 (3 H )-ketone 6.7 g, yield 68%.

[0054] 1 H NMR (400 MHz, CDCl 3 ): δ 7.99-7.97 (d, J = 7.6 Hz, 2H), 7.66-7.63(t, J = 7.4 Hz, 1H), 7.54-7.50 (t, J = 7.6 Hz, 2H), 5.83-5.81 (m, 1H), 2.64-2.56 (m, 3H), 2.50-2.44 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 194.3, 176.2, 134.2, 133.6, 129.0, 128.7, 78.2, 26.8, 24.9.

Embodiment 2

[0056] Add 234 mg of raw material 4-(2,4,6-trimethylbenzoyl)butyric acid, 738 mg of catalyst tetra-n-butylammonium iodide and 8 mL of acetonitrile, 2 mL of methanol into a diaphragmless electrolyzer as a mixture Solvent, and then insert the platinum sheet electrode, pass the current density of 8 mA / cm 2 constant current at 40 o The reaction was stirred under C; the reaction was tracked by thin layer chromatography, and the solvent was rotated under vacuum after the reaction was completed, and then the product 5-(2,4,6-trimethylbenzoyl)dihydrofuran-2 (3 H )-ketone 174 mg, yield 75%.

[0057] 1 H NMR (400 MHz, CDCl 3 ): δ 6.88 (s, 2H), 5.28-5.24 (dd, J = 5.0 Hz,8.3 Hz, 1H), 2.61-2.45 (m, 3H), 2.37-2.33 (m, 1H), 2.29 (s, 3H), 2.24 (s,6H); 13 C NMR (100 MHz, CDCl 3 ): δ 205.7, 176.1, 140.0, 135.0, 134.1, 128.8, 81.7, 26.9, 24.6, 21.0, 19.5.

Embodiment 3

[0059] Add 198 mg of raw material 5-oxo-5-(2-thienyl)pentanoic acid, 750 mg of catalyst NaI, and 5 mL of solvent ethanol to the electrolytic cell without a diaphragm, and then insert a graphite electrode with a current density of 6 mA / cm 2 constant current at 60 o The reaction was stirred under C; the reaction was tracked by thin-layer chromatography, and the solvent was spun off under vacuum after the reaction was completed, and then the product 5-(thiophene-2-carbonyl)dihydrofuran-2(3 H )-ketone 153 mg, yield 78%.

[0060] 1 H NMR (400 MHz, CDCl 3 ): δ 7.92-7.91 (d, J = 3.2 Hz, 1H), 7.79-7.77(d, J = 4.7 Hz, 1H), 7.22-7.19 (t, J = 4.3 Hz, 1H), 5.59-5.56 (m, 1H), 2.67-2.55 (m, 3H), 2.53-2.48 (m, 1H); 13 C NMR (100 MHz, CDCl 3 ): δ 187.9, 176.1, 140.1, 135.6, 133.9, 128.6, 79.2, 26.8, 25.4.

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Abstract

The invention discloses a method for electrochemically synthesizing α-acyloxy ketones. The method utilizes an electrochemical method to perform oxidative coupling reaction on ketones and carboxylic acids in raw materials to directly synthesize α-acyloxy ketones with various structures. The synthesis method has the advantages of simple operation, mild conditions, environmental protection, stability and high efficiency, easy control and large-scale production, avoids the use of excessive oxidant in the reaction process, is more general and direct, and has a wide range of applications.

Description

【Technical field】 [0001] The invention belongs to the field of organic synthesis, and in particular relates to a method for electrochemically synthesizing alpha-acyloxy ketones. 【Background technique】 [0002] α-Acyloxyketone compounds widely exist in natural products or medicines, and often serve as key structural skeletons of physiologically active molecules and drug molecules, with high biological activity and potential application value (Fukuda, T.; Matsumoto, A. ; Takahashi, Y.; Tomoda, H.; Omura, S. J. Antibiot. 2005, 58,252; Yan, B.-F.; Fang, S.-T.; Li, W.-Z.; Liu, S.-J .; Wang, J.-H.; Xia, C.-H. Nat. Prod. Res. 2015, 29, 2013.). As its α-functionalization reaction plays an increasingly prominent role in organic synthesis, its synthesis method has become the focus of research by chemists in recent years. At present, the commonly reported synthesis methods of α-acyloxyketone compounds are as follows: In 2009 and 2011, Ishihara’s research group used hypervalent iodine...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C25B3/02C25B3/23
CPCC25B3/23
Inventor 张胜李丽君徐坤王会巧张旭徐学锋王志强柳文敏桑志培李亭
Owner NANYANG NORMAL UNIV