Preparation method of isocoumarin derivative

A technology for isocoumarin and derivatives, which is applied in the field of preparation of isocoumarin derivatives, can solve the problems of single reaction mode and less fluorine-containing isocoumarins, etc., and achieves the effects of simple operation, diverse types and rich development.

Active Publication Date: 2020-05-12
SUZHOU UNIV
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In the prior art, some documents have reported the synthesis method of isocoumarin, but the reaction mode is single, and the method for synthesizing fluorine-containing isocoumarin is less reported

Method used

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  • Preparation method of isocoumarin derivative
  • Preparation method of isocoumarin derivative
  • Preparation method of isocoumarin derivative

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preparation example Construction

[0033] The invention provides a preparation method of isocoumarin derivatives, comprising: sequentially adding benzoic acid derivatives, pentamethylcyclopentadiene iridium dichloride dimer, dipotassium hydrogen phosphate, and silver acetate into a glass reaction tube and bromotrifluoroacetone, ethyl bromopyruvate, bromoacetophenone, or bromoacetone, etc., put into a stirring bar, use trifluoroethanol as a solvent, and fix the glass reaction tube in a heating stirrer for Stirring, after the reaction is completed, the product is subjected to column chromatography separation and purification treatment to obtain isocoumarin derivatives.

[0034] The reaction process of above-mentioned technical scheme can be expressed as:

[0035]

Embodiment 1

[0039] This implementation case shows a preparation method of isocoumarin derivatives according to the following steps: using 3-methylbenzoic acid as a raw material, the reaction formula is as follows:

[0040]

[0041] (1) Add 0.0326 grams (0.24 mmol) of m-toluic acid, 0.0040 grams (0.005 mmol) of pentamethylcyclopentadiene iridium dichloride dimer, 0.0174 grams (0.1 mmol) of dipotassium hydrogen phosphate, 0.040 g (0.24 mmol) of silver acetate, 0.0382 g (0.2 mmol) of bromotrifluoroacetone and 1 mL of trifluoroethanol were reacted at 140°C for 24 hours;

[0042] ⑵ TLC ​​tracking reaction until the complete end;

[0043] (3) The crude product obtained after the reaction finishes is separated by column chromatography (petroleum ether: ethyl acetate=30:1),

[0044] The target product was obtained (yield 71%).

[0045] 1 H NMR (400MHz, CDCl 3 )δ8.11(s,1H),7.62(dd,J=7.9,1.3Hz,1H),7.45(d,J=8.0Hz,1H),6.95(s,1H),2.50(s,3H). 13 C NMR (101MHz, CDCl 3 )δ160.0,141.7(q,J C-F =58...

Embodiment 2

[0047] This implementation case shows a kind of preparation method of isocoumarin derivative according to the following steps: using 2-chlorobenzoic acid as raw material, its reaction formula is as follows:

[0048]

[0049] (1) Add 0.0374 grams (0.24 mmol) of 2-chlorobenzoic acid, 0.0040 grams (0.005 mmol) of pentamethylcyclopentadiene iridium dichloride dimer, 0.0174 grams (0.1 mmol) of dipotassium hydrogen phosphate, 0.040 g (0.24 mmol) of silver acetate, 0.0382 g (0.2 mmol) of bromotrifluoroacetone and 1 mL of trifluoroethanol were reacted at 140°C for 24 hours;

[0050] ⑵ TLC ​​tracking reaction until the complete end;

[0051] (3) The crude product obtained after the reaction was separated by column chromatography (petroleum ether:ethyl acetate=30:1) to obtain the target product (yield 61%).

[0052] 1 H NMR (400MHz, CDCl 3 )δ7.70–7.66(m,2H),7.48–7.43(m,1H),6.93(s,1H). 13 CNMR (101MHz, CDCl 3 )δ156.2,143.2(q,J C-F =39.4Hz), 138.2, 137.3, 135.4, 133.7, 126.4, 118.4...

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Abstract

The invention discloses a preparation method of an isocoumarin derivative. The method comprises the following steps: sequentially adding a benzoic acid derivative, a pentamethylcyclopentadiene iridiumdichloride dimer, dipotassium hydrogen phosphate, silver acetate and a brominated raw material into a reaction tube, and reacting at 140 DEG C for 24 hours by using trifluoroethanol as a reaction solvent to obtain the isocoumarin derivative. According to the invention, a benzoic acid derivative is used as an initiator, so that raw materials are easy to obtain and various in variety; the product obtained by the method is various in type, can be directly applied to synthesis of drug molecules, and can also be applied to other further reactions; and the synthetic route is safe and feasible, thecost is low, the reaction operation and the post-treatment process are simple, the selectivity is good, side reactions are few, and an amplification reaction can be carried out.

Description

technical field [0001] The present invention relates to the direct synthesis of isocoumarin derivatives from benzoic acid derivatives. Background technique [0002] As important components of natural lactones with various biological activities, and as key intermediates in the synthesis of heterocycles, the synthesis of isocoumarin derivatives has received extensive attention in medicinal and synthetic chemistry. [0003] Isocoumarin derivatives usually have significant biological and pharmacological activities. Scientific research has shown that compounds containing isocoumarin skeletons have a wide range of biological activities, such as anti-allergic, anti-bacterial, anti-fungal, anti-tumor, anti-inflammatory and other activities. In the field of fluorination research, about 30% of agricultural chemicals and 20% of all drugs contain fluorine, especially the substances containing trifluoromethyl functional groups have an irreplaceable role in medicinal chemistry, life scie...

Claims

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Application Information

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IPC IPC(8): C07D311/76C07D311/92C07D493/04
CPCC07D311/76C07D311/92C07D493/04
Inventor 赵应声周科含
Owner SUZHOU UNIV
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