Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation

A technology for decarboxylation of keto acids and decarbonylation of aldehydes, applied in the field of synthesis of aryl ketone derivatives, can solve the problems of stoichiometric consumption of organometallic reagents, many reaction steps, large environmental impact, etc., and achieves low cost and simple steps. , the effect of low cost

Active Publication Date: 2020-04-24
XIANGTAN UNIV
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Problems solved by technology

[0004] In view of the deficiencies in the existing method for synthesizing aryl ketone derivatives, such as the large consumption of Lewis acid, many by-products, great impact on the environment, many reaction steps, and the need to consume stoichiometric organometallic rea

Method used

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  • Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation
  • Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation
  • Method for preparing aryl ketone based on iron-catalyzed free radical-free radical coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Benzoylformic acid (30.0mg, 0.2mmol), Fe(acac) 3 (21.2mg, 0.06mmol), isobutyraldehyde (72.0mg, 1.0mmol), DTBP (58.5mg, 0.4mmol), K 2 S 2 o 8 (81.1 mg, 0.3 mmol) and a stirring bar were placed in a reaction tube, and 1 mL of ethyl acetate was added as a solvent to seal the reaction tube. Put the reaction tube into an oil bath at 120° C., start stirring, and react at a constant temperature for 12 hours. After cooling the reaction mixture to room temperature, the solid residue was filtered through a short plug of silica gel and washed with 10 mL of ethyl acetate. After evaporating the solvent in vacuo, the crude product was subjected to column chromatography with petroleum ether: ethyl acetate = 30:1 as the eluent to obtain a pure product. Colorless oil, yield 74%. 1 H NMR (400MHz, CDCl 3 )δ7.96(d, J=7.6Hz, 2H), 7.57-7.54(m, 1H), 7.49-7.45(m, 2H), 3.60-3.53(m, 1H), 1.22(d, J=6.8Hz ,6H); 13 C NMR (100MHz, CDCl 3 )δ204.6, 136.2, 132.8, 128.6, 128.3, 35.4, 19.2; -1 ...

Embodiment 2

[0032] Benzoylformic acid (30.0mg, 0.2mmol), Fe(acac) 3 (21.2mg, 0.06mmol), 2-methylbutanal (86.0mg, 1.0mmol), DTBP (58.5mg, 0.4mmol), K 2 S 2 o 8 (81.1 mg, 0.3 mmol) and a stirring bar were placed in a reaction tube, and 1 mL of ethyl acetate was added as a solvent to seal the reaction tube. Put the reaction tube into an oil bath at 120° C., start stirring, and react at a constant temperature for 12 hours. After cooling the reaction mixture to room temperature, the solid residue was filtered through a short plug of silica gel and washed with 10 mL of ethyl acetate. After the solvent was evaporated in vacuo, the crude product was subjected to column chromatography with petroleum ether: ethyl acetate = 50:1 as the eluent to obtain a pure product. Yellow oil, yield 65%. 1 H NMR (400MHz, CDCl 3 )δ7.96(d, J=7.6Hz, 2H), 7.56(t, J=7.4Hz, 1H), 7.47(t, J=7.6Hz, 2H), 3.45-3.37(m, 1H), 1.88- 1.79(m,1H),1.55-1.40(m,1H),1.20(d,J=7.2Hz,3H),0.92(t,J=7.4Hz,3H); 13 C NMR (100MHz, CDCl...

Embodiment 3

[0034] Benzoylformic acid (30.0mg, 0.2mmol), Fe(acac) 3 (21.2mg, 0.06mmol), 2-methylpentanal (100.0mg, 1.0mmol), DTBP (58.5mg, 0.4mmol), K 2 S 2 o 8 (81.1 mg, 0.3 mmol) and a stirring bar were placed in a reaction tube, and 1 mL of ethyl acetate was added as a solvent to seal the reaction tube. Put the reaction tube into an oil bath at 120° C., start stirring, and react at a constant temperature for 12 hours. After cooling the reaction mixture to room temperature, the solid residue was filtered through a short plug of silica gel and washed with 10 mL of ethyl acetate. After evaporating the solvent in vacuo, the crude product was subjected to column chromatography with petroleum ether: ethyl acetate = 70:1 as the eluent to obtain a pure product. Yellow oil, yield 63%. 1 H NMR (400MHz, CDCl 3 )δ7.97-7.95(m,2H),7.56(t,J=7.1Hz,1H),7.47(t,J=7.6Hz,2H),3.43-3.45(m,1H),1.82-1.75(m ,1H),1.43-1.25(m,3H),1.19(d,J=6.8Hz,3H),0.91(t,J=7.2Hz,3H); 13 C NMR (100MHz, CDCl 3 )δ204.6, 13...

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Abstract

The invention discloses a method for preparing an aryl ketone derivative based on a free radical-free radical cross-coupling reaction such as ketonic acid decarboxylation and fatty aldehyde de-carbonylation. The method comprises the following steps: reacting aryl-substituted ketonic acid with fatty aldehyde under the catalytic action of ferric triacetylacetonate to generate an aryl ketone derivative; the gram-grade reaction can be realized by the method only by using 3mol% of an iron catalyst; and the method has the advantages of no need of consumption of a large amount of a Lewis acid catalyst or a stoichiometric organic metal reagent, mild reaction conditions, one-step reaction, few by-products, wide substrate application range and scalable reaction, and overcomes the defects of large catalyst consumption, insufficient functional group tolerance, many by-products and the like in the prior art.

Description

technical field [0001] The invention relates to a synthesis method of aryl ketone derivatives, in particular to a method for preparing aryl ketone derivatives based on free radical cross-coupling reactions of iron-catalyzed decarboxylation of ketoacids and decarbonylation of aliphatic aldehydes, belonging to the pharmaceutical center body synthesis and fine organic synthesis. Background technique [0002] Aryl ketones are an important class of organic compounds that widely exist in biologically active substances such as natural products and pharmaceutical intermediates (molecular structure formula below). The most common method for the preparation of aryl ketones is the Friedel-Crafts acylation reaction. However, this method often needs to consume a large amount of Lewis acid catalysts, and is prone to produce a large number of by-products, which has a great impact on the environment. And this reaction has higher requirements on the activity of arenes, and it is difficult ...

Claims

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Application Information

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IPC IPC(8): C07B61/00C07C45/54C07D333/22C07C49/76C07C49/792C07C49/798C07C49/84C07C49/825C07C49/807C07C49/788
CPCC07B61/02C07C45/54C07D333/22C07C2601/08C07C2601/14C07C2601/16C07C2601/02C07C2603/74C07C49/76C07C49/792C07C49/798C07C49/84C07C49/825C07C49/807C07C49/788
Inventor 龚行赵御含李乐松
Owner XIANGTAN UNIV
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