A kind of preparation method of isoxaflutole key intermediate
A technology of isoxaflutole and intermediates, applied in the field of pesticide chemistry, can solve problems such as difficult control and impact on industrialization, achieve mild reaction, increase yield and purity, and reduce production costs
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Embodiment 1
[0029] Preparation of Intermediate I:
[0030]
[0031] Step (1): Preparation of intermediate I, under nitrogen protection, 70.27g (0.3mol) 1-(2-(methylthio)-4-(trifluoromethyl)phenyl)ethanone was mixed with 21.13g (0.315mol) cyclopropanecarbonitrile was dissolved in 182.8g of 2-methyl-tetrahydrofuran, 31.71g (0.33mol) of sodium tert-butoxide was added, the temperature of the mixture was raised to 40°C for 3 hours, the temperature was lowered to room temperature, and 60.26g was added. (0.33mol) 20% hydrochloric acid aqueous solution was adjusted to neutral pH to stop the reaction, the aqueous phase was separated, and the organic phase was concentrated to obtain 3-amino-3-cyclopropyl-1-(2-(methylthio) as a yellow liquid) -4-(trifluoromethyl)phenyl)-2-ene-1-propanone is dissolved in 2-methyl-tetrahydrofuran, namely intermediate I, qualitative content 99%, weight yield 99%, 1 H NMR (400MHz, DMSO): δ10.06(s, 1H), 7.92(s, 1H), 7.60(d, J=7.8Hz, 1H), 7.51-7.43(m, 2H), 5.15(d, J ...
Embodiment 2
[0034] Step (1): Preparation of Intermediate I, under nitrogen protection, 281.09g (1.2mol) 1-(2-(methylthio)-4-(trifluoromethyl)phenyl)ethanone was mixed with 82.12g (1.224mol) cyclopropanecarbonitrile was dissolved in 618g 2-methyl-tetrahydrofuran, 126.85g (1.32mol) sodium tert-butoxide was added, the temperature of the mixture was increased to 45°C for 2.5 hours, the temperature was lowered to room temperature, 240.9g ( 1.32mol) 20% hydrochloric acid aqueous solution adjusts pH value to neutrality to stop the reaction, separates the water phase, and the organic phase is used for feeding step (2), and the qualitative content is 99%;
[0035] Step (2): Preparation of 1-cyclopropyl-3-(2-(methylthio)-4-(trifluoromethyl)phenyl)propyl-1,3-dione, in step (1) In the organic phase, add 175.2 g (1.44 mol) of 30% aqueous hydrochloric acid solution, raise the temperature to 50° C. for 3 hours, separate the aqueous phase, and concentrate the organic phase to obtain a pale yellow solid 1...
Embodiment 3
[0037]Step (1): Preparation of intermediate I, under nitrogen protection, 140.54g (0.6mol) 1-(2-(methylthio)-4-(trifluoromethyl)phenyl)ethanone was mixed with 44.28g (0.66mol) cyclopropanecarbonitrile was dissolved in 562.16g of 2-methyl-tetrahydrofuran, 74.96g (0.78mol) of sodium tert-butoxide was added, the temperature of the mixture was raised to 50°C for 3 hours, the temperature was lowered to room temperature, and 109.5g was added. (0.6mol) 20% hydrochloric acid aqueous solution adjusts the pH value to neutrality and stops the reaction, separates the aqueous phase, and concentrates the organic phase to obtain the intermediate I of the yellow liquid, the qualitative content is 98%, and the weight yield is 98%;
[0038] Step (2): Preparation of 1-cyclopropyl-3-(2-(methylthio)-4-(trifluoromethyl)phenyl)propyl-1,3-dione, 176.64 g (0.576 g) mol) Intermediate I was dissolved in 2-methyl-tetrahydrofuran, 91.13g (0.749mol) of 30% aqueous hydrochloric acid was added, the temperatu...
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