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Method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole

A synthesis method and intermediate technology, applied in the field of compound synthesis, can solve the problems of reducing the number of reaction steps and not fundamentally solving the problems of scarce raw materials, and achieve the effects of simplified operation, high economic value and social significance, and reduced production cost.

Active Publication Date: 2010-10-06
SHANDONG BOYUAN PHARM CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0017] The raw materials used in this method are the same as the previous method, but the reaction steps are reduced, and the problem of rare raw materials is not fundamentally solved.

Method used

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  • Method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole
  • Method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole
  • Method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] (1) Preparation of 3-methyl salicylaldehyde

[0031]

[0032] Put 5.76g of magnesium chips and 57.6g of anhydrous methanol into a 500ml four-neck flask, heat to reflux, and a large number of bubbles are formed. When the solution becomes turbid, add 50ml of toluene and continue to reflux. When the magnesium chips basically disappear, add toluene 50ml, continued to reflux for half an hour, put in 200ml of toluene, added dropwise 21.6g of o-cresol, heated up and distilled methanol until the temperature of the reactant reached 95°C. Keep at 95°C, add 24g of polyoxymethylene in batches, add 1 hour, distill off the generated methanol at the same time, continue to keep warm for 1 hour after the addition, track the plate, cool down after the reaction is complete, add 10% hydrochloric acid 175±10 gram, stirred, separated into layers, the toluene layer was washed twice with water, and desolvated under reduced pressure to obtain 24 g of a red oily substance with a mass percenta...

Embodiment 2

[0046] (1) The preparation of 3-methyl salicylaldehyde is the same as in Example 1.

[0047] (2) 24g of the product from the previous step was dissolved by adding 200ml of ethanol, adding 10g of sodium carbonate, slowly adding 122g of hydrogen peroxide with a mass percent content of 5%, and kept at 30°C for 5 hours, and the product was directly transferred to a 1L autoclave without separation , add 100ml of dichloromethane, 100ml of DMF, 8g of sodium carbonate, and 2g of tetrabutylammonium bromide, seal the autoclave, heat to 110°C for 2 hours, cool to room temperature, and open the pressure relief valve to release the pressure. Then the autoclave was opened, and the reactant was distilled to remove the low-boiling solvent, and water was added for azeotropic distillation to obtain 12 g of a colorless oily liquid with a normalized purity of 97.5% and a yield of 54%.

[0048] (3) Dissolve 12 g of the product from the previous step in 50 ml of toluene, add 21 g of phosphorus pent...

Embodiment 3

[0052] (1) The preparation of 3-methyl salicylaldehyde is the same as in Example 1.

[0053] (2) Preparation of 4-methylbenzodioxol

[0054] Add 200ml of methanol to dissolve 24g of the product from the previous step, add 16.8g of sodium bicarbonate, slowly add 136g of hydrogen peroxide with a mass percentage of 5%, keep it at 40°C for 4 hours, and transfer the product directly into a 1L autoclave without separation. Add 100ml of dichloromethane, 100ml of DMF, 6.4g of NaOH, and 2g of tetrabutylammonium bromide, seal the autoclave, heat to 90°C for 3 hours, cool to room temperature, and open the pressure relief valve to release the pressure. Then the autoclave was opened, and the reactant was distilled to remove the low-boiling solvent, and water was added for azeotropic distillation to obtain 13.6 g of a colorless oily liquid, with a normalized purity of 98.5% and a yield of 62.5%.

[0055] (3) Preparation of 4-methyl-2,2-dichlorobenzodioxol

[0056] Dissolve 13.6 g of the p...

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Abstract

The invention discloses a method for synthesizing fludioxonil intermediate 4-aldehyde-2,2-difluorobenzodioxole. The method comprises the following steps of: performing o-orientating formylation on o-cresol serving as an initiative raw material to obtain 3-methylsalicylaldehyde, converting the 3-methylsalicylaldehyde into 3-mehtylpyrocatechol through Dakin reaction, directly reacting the 3-mehtylpyrocatechol with dichloromethane or dibromomethane to generate 4-methylbenzodioxole without separation and purification, and performing three-step reaction of chlorination, fluoro and oxidation on the 4-methylbenzodioxole to generate a product. The cheap o-cresol is used as the initiative raw material, and the obtained 3-mehtylpyrocatechol directly enters the next reaction without separation, so the production cost is greatly reduced; phosphorus pentachloride is used as a chlorination reagent in the chlorination link so as to avoid the use of chlorine and reduce the risk of causing environmental pollution; and the methyl is converted into aldehyde group through the oxidation reaction so as to avoid a route of chlorination hydrolysis, simplify the operation, reduce the environment-friendly pressure and gain higher economic value and social meaning.

Description

technical field [0001] The invention relates to a synthesis method of a compound, in particular to a synthesis method of an intermediate 4-formyl 2,2-difluorobenzodioxol of fludioxonil. Background technique [0002] Fludioxonil is a new type of non-systemic fungicide with epoch-making significance. Its trade name is Shilax. It is an efficient, safe and new type of agricultural fungicide. It is currently one of the largest seed treatment agents in the world. Due to its low dosage, minimal toxicity and long duration, it is rated as a zero-risk product by the US Environmental Protection Agency, and has a very broad market prospect. [0003] 4-Formyl-2,2-difluorobenzodioxole is the key intermediate for the synthesis of fludioxonil, the English name is 2,2-Difluorobenzodioxole-4-carboxaldehyde; the molecular formula is C 8 h 4 f 2 o 3 ; Molecular weight is 186.11; Structural formula is: [0004] CAS#: 119895-68-0; [0005] The reported synthetic methods of 4-formyl-2,2-di...

Claims

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Application Information

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IPC IPC(8): C07D317/46
Inventor 张宏川刘凡磊闫兴蓬
Owner SHANDONG BOYUAN PHARM CO LTD
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