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Synthetic method of benzodioxole derivative

A synthesis method and derivative technology, applied in the field of synthesis of piperonyl ring derivatives, can solve the problems of high price, purity only up to 95%, hindering the application of pharmaceutical intermediates, etc., achieve low cost, short synthesis steps, and good application prospects Effect

Pending Publication Date: 2021-02-12
成都伊诺达博医药科技有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, currently commercially available 7-bromobenzo[D][1,3]dioxol-4-ones are expensive, such as 1-(7-bromobenzo[d][1,3 ]Dioxol-4-yl)ethan-1-one (CAS: 1892297-18-6) has a market price of hundreds of dollars per gram, and the purity only reaches 95%~98%, which hinders its Further application as a pharmaceutical intermediate

Method used

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  • Synthetic method of benzodioxole derivative
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Experimental program
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Embodiment 1

[0022] Embodiment 1,2, the synthesis of 3-dihydroxyacetophenone (formula I compound)

[0023] Zinc dichloride (34.1g, 0.25mol) and acetic acid (9.0g, 0.15mol) were added in the reaction flask, heated to 80°C and stirred to dissolve, then added pyrocatechol (11g, 0.1mol), and then heated to Reaction at 100°C for 4h. Cool down to room temperature, add water (200ml) to quench the reaction, extract with ethyl acetate (100ml×3 times), combine the organic phases, concentrate and dry to obtain the crude product, add n-heptane (100ml), stir and beat at room temperature for 1h, filter, filter The cake was dried to obtain 12.2 g of 2,3-dihydroxyacetophenone with a yield of 80.3% and a purity of 98.8%.

Embodiment 2

[0024] Embodiment 2,2, the synthesis of 3-dihydroxyacetophenone (formula I compound)

[0025] Aluminum trichloride (33.34g, 0.25mol), acetyl chloride (9.42g, 0.12mol) and dichloromethane (550ml) were added to the reaction flask, stirred for 30 minutes, then added catechol (11g, 0.1mol ), react at room temperature for 3h after the addition. Add 2N hydrochloric acid (200ml) to quench the reaction, separate the layers, wash the organic phase with tap water (150ml×2), and dry over anhydrous sodium sulfate. After filtration, the filtrate was concentrated to dryness to obtain a crude product, which was added with n-heptane (100ml), stirred and beaten at room temperature for 1 hour, filtered, and the filter cake was dried to obtain 12.7g of 2,3-dihydroxyacetophenone with a yield of 83.6% and a purity of 98.6%.

Embodiment 3

[0026] Embodiment 3, the synthesis of 2,3-dihydroxyl-4-bromoacetophenone (formula II compound)

[0027] Add tert-butylamine (28.5g, 0.39mol) and toluene (100ml) into the reaction flask, cool down to -10~-15°C, add bromine (33.6g, 0.21mol) dropwise, continue to cool down to -30~ At -40°C, a solution of 2,3-dihydroxyacetophenone (20g, 0.13mol) in toluene (100ml) was added dropwise, and kept at -30~-40°C for 2h after dropping. Warm up to room temperature, and filter to obtain the crude product. Add 250ml of petroleum ether, heat to reflux for 1h, lower to room temperature and stir for 2h, filter, wash the filter cake with a small amount of petroleum ether, and dry to obtain 26.5g of 2,3-dihydroxy-4-bromoacetophenone with a yield of 87.2%. 98.3% purity.

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Abstract

The invention provides a synthetic method of a benzodioxole derivative, which is used for preparing a 7-bromobenzo [ D ] [1,3] dioxol-4-one benzodioxole derivative through acylation reaction, substitution reaction and reaction with dihalomethane. The method disclosed by the invention has the advantages of high yield, high purity, short synthesis steps, conventional and easily available starting materials, low cost and environmental friendliness, and has a good industrial application prospect.

Description

technical field [0001] The invention belongs to the technical field of synthesis, and in particular relates to a synthesis method of piperonyl ring derivatives. Background technique [0002] The chemical name of the piperonyl ring is 1,3-benzodioxazole, which is an important intermediate for the synthesis of the pesticide synergist piperonyl butoxide and the drug berberine, and can be introduced into its benzene ring and methylene with various The group derived a series of high value-added fine chemicals, which are widely used in spices, pesticides, medicine and other fields. [0003] The piperonyl ring structural unit is closely related to antitumor activity, and its derivatives have good cytotoxic activity against human colon cancer cells and multidrug-resistant nasopharyngeal cancer cells, and their in vivo drug effects have also shown excellent tumor inhibitory activity. 7-Bromobenzo[D][1,3]dioxol-4-ones belong to piperonyl derivatives and are key intermediates in drug...

Claims

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Application Information

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IPC IPC(8): C07D317/62
CPCC07D317/62Y02P20/55
Inventor 刘正超罗红刘维文张菊华王婷
Owner 成都伊诺达博医药科技有限公司