Synthesis method of coumarin derivatives

A technology of coumarins and a synthesis method is applied in the field of synthesizing coumarin derivatives, can solve the problems of long time, need to stir the reaction overnight, or even react for several days, achieves less catalyst usage, improves production efficiency, The effect of short reaction time

Active Publication Date: 2020-09-15
THE KEY LAB OF CHEM FOR NATURAL PROD OF GUIZHOU PROVINCE & CHINESE ACADEMY OF SCI
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

Among them, the Pechmann method using phenols and β-ketoesters as reaction raw materials is the most widely used, and the catalyst used is H 2 SO 4 , FeCl 3 , ZnCl 2 , POCl 3 , AlCl 3 , HCl, phosphoric acid and trifluoroacetic acid, etc., but there are some limitations, such as: a. The catalyst needs to be used in excess (5-12 equivalents) (Chem.Ber., 1884,17,929; J.Org.Chem., 1962, 27,3703); b. The reaction time is too long, and it needs to be stirred and reacted overnight, or even reacted for several days (Tetrahedron Lett., 2002, 43, 9195)

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  • Synthesis method of coumarin derivatives
  • Synthesis method of coumarin derivatives
  • Synthesis method of coumarin derivatives

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Experimental program
Comparison scheme
Effect test

Embodiment 1

[0027] Embodiment 1: a kind of synthetic method of coumarin derivatives:

[0028] Add 0.6mmol of PPA and 0.3mL of solvent DMF into the round bottom flask, then add 0.3mmol of salicylaldehyde and 1.2mmol of acetic anhydride in sequence, and stir in an oil bath at 145°C under nitrogen protection for 3h; Wash the organic layer with water and saturated sodium chloride solution, then dry and wash the organic layer with anhydrous sodium sulfate, filter, and the residue after the filtrate is concentrated under reduced pressure is subjected to silica gel column chromatography (V 石油醚 / V 乙酸乙酯 =50:1) separation and purification to obtain coumarin derivative I-1 with a yield of 91%.

[0029] The nuclear magnetic resonance (NMR) of the prepared coumarin derivatives (I-1) 1 H NMR and 13 C NMR) detection data are: 1 HNMR (600MHz, CDCl 3 )δ7.73(d,J=9.5Hz,1H),7.58–7.53(m,1H),7.51(dd,J=7.7,1.4Hz,1H),7.36(d,J=8.3Hz,1H), 7.32–7.28(m,1H),6.45(d,J=9.5Hz,1H). 13 C NMR (151MHz, CDCl 3 )δ160.8...

Embodiment 2

[0030] Embodiment 2: a kind of synthetic method of coumarin derivatives:

[0031] Add 0.6mmol of PPA and 0.3mL of solvent DMF into the flask, then add 0.3mmol of 4-fluorosalicylaldehyde and 1.2mmol of acetic anhydride in sequence, and stir in an oil bath at 145°C for 4h under nitrogen protection; after the reaction, extract with ethyl acetate twice, Wash the organic layer with water and saturated sodium chloride solution successively, then dry and wash the organic layer with anhydrous sodium sulfate, filter, and the residue after the filtrate is concentrated under reduced pressure is subjected to silica gel column chromatography (V 石油醚 / V 乙酸乙酯 =40:1) separation and purification to obtain coumarin derivative I-2 with a yield of 80%.

[0032] The nuclear magnetic resonance (NMR) of the prepared coumarin derivatives (I-2) 1 H NMR and 13 C NMR) detection data are: 1 HNMR (600MHz, CDCl 3 )δ7.71(d, J=9.6Hz, 1H), 7.50(dd, J=8.5, 6.0Hz, 1H), 7.10–7.01(m, 2H), 6.40(d, J=9.6Hz, 1H)...

Embodiment 3

[0033] Embodiment 3: a kind of synthetic method of coumarin derivatives:

[0034] Add 0.6mmol of PPA and 0.3mL of solvent DMF into the flask, then add 0.3mmol of 5-chlorosalicylaldehyde and 1.2mmol of acetic anhydride in sequence, and stir in an oil bath at 145°C under nitrogen protection for 3h; after the reaction, extract with ethyl acetate twice, Wash the organic layer with water and saturated sodium chloride solution successively, then dry and wash the organic layer with anhydrous sodium sulfate, filter, and the residue after the filtrate is concentrated under reduced pressure is subjected to silica gel column chromatography (V 石油醚 / V 乙酸乙酯 =30:1) separation and purification to obtain coumarin derivative I-3 with a yield of 82%.

[0035] The nuclear magnetic resonance (NMR) of the prepared coumarin derivatives (I-3) 1 H NMR and 13 C NMR) detection data are: 1 HNMR (600MHz, DMSO) δ8.00(d, J=9.6Hz, 1H), 7.82(d, J=2.5Hz, 1H), 7.63(dd, J=8.8, 2.6Hz, 1H), 7.42(d, J=8.8Hz, 1...

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Abstract

The invention provides a synthesis method of coumarin derivatives. The synthesis method comprises the following steps: adding polyphosphoric acid PPA and a solvent N,N-dimethylformamide DMF, sequentially adding substituted salicylaldehyde and acetic anhydride, and carrying out a heating stirring reaction for 3-6 h under nitrogen protection; and after the reaction is finished, separating and purifying to obtain the coumarin derivative pure products. The synthesis method disclosed by the invention is disclosed for the first time, is short in reaction time, simple to operate, low in catalyst usage amount, cheap, easy to obtain and relatively good in derivative yield, not only provides a new method for synthesizing coumarin derivatives, but also provides more possibilities for large-scale production of products and improvement of production efficiency.

Description

technical field [0001] The invention belongs to the technical field of chemical synthesis, and in particular relates to a synthesis method of coumarin derivatives. Background technique [0002] Coumarin is a class of natural products that widely exist in nature, and its core structure is benzoα-pyrone. Studies have found that coumarin has biological activities such as antibacterial, anticancer, antioxidative, anti-inflammatory, hypoglycemic, anticoagulant, antitumor, antiviral, and herbicidal, and is fully used in medicine, spices, pesticides, and fluorescence dyes and many other fields. Coumarin derivatives have many types of molecular structures, a wide range of biological activities, and unique mechanisms of action. Although it is distributed in natural plants, its content is not much and its sources are limited. Therefore, modifying the structure of coumarin and artificially synthesizing coumarin compounds have become a research hotspot in related fields. There are ma...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/10C07D311/14C07D311/16C07D311/18B01J27/16
CPCC07D311/10C07D311/14C07D311/16C07D311/18B01J27/16
Inventor 杨小生杨礼寿王恩花杨倩彭梅严艳芳李立朗廖秀高明潘雄
Owner THE KEY LAB OF CHEM FOR NATURAL PROD OF GUIZHOU PROVINCE & CHINESE ACADEMY OF SCI
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