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Picoxystrobin preparation method

A technology of picoxystrobin and oxygen, which is applied in the field of preparation of the fungicide picoxystrobin, can solve the problem of low reaction yield, low yield of picoxystrobin phenyl acetate, and influence on the final product yield and other problems, to achieve the effect of mild reaction conditions, good selectivity, and less waste

Active Publication Date: 2014-03-12
上海禾本药业股份有限公司
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0010] (3) WO1997012864 discloses a method for preparing the key intermediate 2-(6-trifluoromethylpyridine-2-oxymethyl)methyl phenylacetate, 3-isochromone is treated with sodium hydroxide to form bis Sodium salt, add N-methylpyrrolidone (NMP) as a solvent to react with 2-chloro-6-trifluoromethylpyridine after azeotroping with water, and then etherify with dimethyl sulfate to obtain the product, the reaction yield is generally low , the best yield is only 62%, and the product content is only 32.3%, and column chromatography is required to obtain pure product, which does not have industrial value
[0012] The inventor found after research that one of the reasons for the low yield of picoxystrobin in the above preparation method is the compound compound (IV) 2-[2′-(6′-trifluoromethylpyridin-2-oxyl) Methyl] the productive rate of methyl phenylacetate is low, and it has directly influenced the yield of final product

Method used

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Experimental program
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Embodiment 1

[0050] 1), 44.4 grams (0.3mol) of compound (I) 3-isochromone was dissolved in a mixture of 45 ml of methanol and 150 ml of toluene, cooled to below 5°C, and 46 ml (0.63mol) was added dropwise under control of 10°C Thionyl chloride, the tail gas was absorbed with 30% hydrogen peroxide, and after the addition was completed, the temperature was naturally raised to room temperature and continued to stir for 2 hours. Control the temperature below 30°C, depressurize the water pump, add hydrogen peroxide absorption liquid into the safety bottle connected to the water pump, and remove low boiling substances. The remaining toluene liquid was washed successively with 25 ml of water and 25 ml of saturated aqueous sodium bicarbonate solution, and the toluene was concentrated and recovered to obtain 62.7 g of crude product of compound (III) (2′-halomethyl)phenylacetate methyl ester, which can be directly used in the next step reaction.

[0051]

[0052] 2) Suspend 48.9 g (0.3 mol) of c...

Embodiment 2

[0058] Embodiment 2 (comparative experiment with embodiment 1 step 2)

[0059] 1.63 g (0.01 mol) of compound (II) 6-trifluoromethyl-2-hydroxypyridine was dissolved in 10 ml of DMF, 1.5 g (0.011 mol) of anhydrous potassium carbonate was added, and stirred at room temperature for 1 hour. 0.01 mol of compound (III) was added dropwise, and the temperature was controlled below 30°C. After the addition, continue stirring at room temperature for 2 hours, filter, concentrate under reduced pressure to recover DMF, add 20 ml of toluene to the residue, wash with 5 ml of 5% dilute hydrochloric acid and 5 ml of saturated sodium bicarbonate successively, concentrate and recover toluene, column chromatography (acetic acid Ethyl ester:petroleum ether=1:5) to obtain 2.54 g of compound (IV) with a yield of 78.1%. 1 HNMR (CDCl 3 ), δ3.67 (s, 3H), 3.84 (s, 2H), 5.46 (s, 2H), 6.89 (d, 1H), 7.23-7.31 (m, 4H), 7.51-7.53 (m, 1H), 7.66-7.70 (m, 1H).

Embodiment 3

[0060] Embodiment 3 (comparative experiment with embodiment 1 step 2)

[0061] 1.63 g (0.01 mol) of compound (II) 6-trifluoromethyl-2-hydroxypyridine was dissolved in 10 ml of DMF, 1.17 g (0.011 mol) of anhydrous sodium carbonate was added, and stirred at room temperature for 2 hours. 0.01 mol of compound (III) was added dropwise, and the temperature was controlled below 30°C. After the addition, continue to stir at room temperature for 8 hours, filter, concentrate under reduced pressure to recover DMF, add 20 milliliters of toluene to the residue, wash with 5 milliliters of 5% dilute hydrochloric acid and 5 milliliters of saturated sodium bicarbonate successively, concentrate and recover toluene, column chromatography (acetic acid Ethyl ester:petroleum ether=1:5) to obtain 1.37 g of compound (IV) with a yield of 42.1%.

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Abstract

The invention discloses a picoxystrobin preparation method. The picoxystrobin preparation method comprises the following steps: (1) dissolving a compound (I)3-isochromanone in methyl alcohol and first inert solvent, and reacting so as to obtain (III) (2-halogenated methyl phenyl) methyl acetate; (2) converting (II) 6-trifluoromethyl-2-pyridone into sodium salt, reacting with quaternary ammonium salt in a polar solvent, and then adding the (III) (2-halogenated methyl phenyl) methyl acetate, thus obtaining (IV) 2-[2'-(6'-tirfluoromethylpyridine-2-oxyl) methyl] phenyl methyl acetate; (3) carrying out aldolization on the (IV) 2-[2'-(6'-tirfluoromethylpyridine-2-oxyl) methyl] phenyl methyl acetate and a formamide compound, and hydrolyzing so as to obtain (V) 2-[2'-(6'-tirfluoromethylpyridine-2-oxyl) methyl] phenyl-3-hydroxyl methyl acetate; and (4) treating the (V) 2-[2'-(6'-tirfluoromethylpyridine-2-oxyl) methyl] phenyl-3-hydroxyl methyl acetate by using alkali and a methylation reagent so as to obtain picoxystrobin.

Description

technical field [0001] The invention relates to a preparation method of the fungicide picoxystrobin. Background technique [0002] Methoxyacrylates (strobilurins) fungicides are a class of low toxicity, high activity and broad-spectrum systemic fungicides, which have protective, therapeutic and eradicating effects. This type of fungicide has good activity against Ascomycetes, Basidiomycetes, Deuteromycetes and Oomycetes, etc. It can be used in grains, rice, grapes, potatoes, vegetables, fruit trees, beans, etc. through stem and leaf treatment and seed treatment. As well as other crops, it can prevent and control powdery mildew, rust, downy mildew and rice blast in various crops. With its unique mechanism of action and extremely friendly attitude towards the environment, methoxyacrylate fungicides have almost covered the major fungicide markets in the world. At present, no less than 10 strobilurins fungicides are active in the international market, and some of them have bec...

Claims

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Application Information

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IPC IPC(8): C07D213/64
CPCC07D213/64
Inventor 张小兵黄秀根李碧澄汪青松叶光武赵泽彬
Owner 上海禾本药业股份有限公司
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