Process for producing insecticide intermediate
A technology of molecular formula and compound, applied in the field of preparation of pesticide intermediates, can solve problems such as oxidation of hydrazine derivatives that have not yet been understood and have not been made
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Embodiment 1
[0048] Preparation of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (Scheme Sc1)
[0049] Ammonia (20 μl 8% ammonia in water) was added to 2-(2,6-dichloro-4-trifluoromethylphenylhydrazono)succinonitrile (0.077 g) and ethanol (1 ml) at 0°C In a mixture with water (0.2 mL), after 10 min the mixture was extracted (dichloromethane) and evaporated to give the title compound (0.076 g, 97% yield) in 98% purity (from Hplc).
Embodiment 2
[0051] Preparation of 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole (Scheme Sc1)
[0052] 2-(2,6-dichloro-4-trifluoromethylphenylhydrazono)succinonitrile (1.0 g) and sodium bicarbonate (40 ml saturated aqueous solution) and dichloromethane (915 ml) at 20°C , and the pH value was 9 and stirred for 3 hours. Sodium carbonate solution was added until the pH was 11 and stirring was continued overnight. A small amount of sodium hydroxide solution was added to make the pH value reach 12, and then a small amount of Aliquat336 (trademark, trioctanoylmethylammonium chloride) was added after 3 hours, and the reaction was completed after 2 hours. The dichloromethane extracts were washed (water and brine), dried (sodium sulfate) and evaporated to give the title compound.
Embodiment 3
[0054] Preparation of 2-(2,6-dichloro-4-trifluoromethylphenylhydrazono)succinonitrile (Scheme Sc2)
[0055] A mixture of 2-(2,6-dichloro-4-trifluoromethylphenylhydrazino)succinonitrile (0.323 g) and copper dichloride (0.175 g) was heated at 60°C in chlorobenzene for 6 hours, filtered and evaporated to give a 7:1 mixture of the title compound and 5-amino-3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole on silica gel Column chromatography eluting with dichloromethane gave the pure title compound as a mixture of cis and trans isomers, NMR (trans isomer) 3.6 (s, 2H), 7.57 (s, 2H), 8.82(s, 1H, available D 2 O exchange), NMR (cis isomer) 3.56 (s, 2H), 7.59 (s, 2H), 8.27 (s, 1H, available D 2 O exchange).
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