Dicyclanil synthesis

Yield:112636-83-6 80 g

Reaction Conditions:

Stage #1:malononitrile with sodium methylate in methanol at 0 - 5; for 0.5 h;
Stage #2:dimethyl N-cyanodithioiminocarbonate in methanol at 0 - 5; for 12 h;
Stage #3:CyclopropylamineFurther stages;

Steps:

1 Example 1:The invention relates to a preparation method of a dicyclanil, Include the following steps:
In the first step, the condensation reaction was carried out. Into a 2L four-necked flask was added 270 g of 500 g of anhydrous methanol and sodium methoxide in methanol. Cool the ice water bath, cool to 0-5°C, add 72.8g malononitrile, stir for 30 minutes, keep the temperature at 0-5°C,In batchwise addition of 146.5 g of N-cyanoimino-S,S-dithiocarbonate dimethyl carbonate, the reaction was stirred at 0-5° C. for 12 h, and the reaction was completed and filtered. The filter cake was washed with 100 mL of cold anhydrous methanol and pumped dry. After being used directly for the next reaction without drying;In the second step, the cyclization reaction, the above wet product was dissolved in 860 g of water and added to a four-necked bottle.After stirring and dissolving, the ice water bath is cooled to 0-5°C, and 1200g of industrial hydrochloric acid is added dropwise. It takes about 4-5 hours to complete the addition.Stir at 0-5 ° C overnight, after the reaction is complete, filter, filter cake washed, washed twice with 10% sodium carbonate, dried, dried in an oven to obtain dried product 157g; In the third step, the cyclopropylation reaction was carried out. In the 2L four-necked bottle, 3157 g of the product in the second step, 1000 g of ethanol and 66.7 g of cyclopropylamine were added, stirred, and the mixture was heated to reflux. The reaction was completed overnight and the reaction was cooled to 0-5. °C, filtration, filter cake washed, drained, dried in an oven to obtain dry product 147g;The fourth step, the oxidation reaction, in the 5L four-necked flask is added to the product of the fourth step 4147g, acetic acid 810g, sodium tungstate 5.5g, heated to 50 ~ 55 °C, while stirring with hydrogen peroxide 230g, plus complete in 50-55 °C reaction 4h, the reaction is complete, recovery of acetic acid under reduced pressure, the residue was added water 800g, cooled to below 10 °C, filtered, the filter cake was washed with water to pH 5-6, drained and used directly in the next reaction without drying;The fifth step, the ammoniation reaction, in the 5L four-necked flask, the fourth step product, ethanol 610g and ammonia water 1450g, 20-25 ° C under stirring for 5h, the reaction is complete, cooled to 5-10 ° C, filtration, filter cake washed, Dry in an oven to obtain 88g of dry product. Dissolve 88g of dry product in 560mL of NN-dimethylamide.Heated to 90 ° C, dissolved, added powdered activated carbon 5g, stirred for 10 minutes, filtered, cooled and placed in the refrigerator overnight, the next day, filtered, filter cake washed with deionized water, drained, dried in an oven, white Powder is 80g.

References:

Shaanxi Qiyuan Technology Development Co., Ltd.;ZHANG, SHU FEN;Shanxi Qiyuan Science And Technology Development Co., Ltd.;Zhang Shufen CN107698519, 2018, A Location in patent:Paragraph 0008

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