Oxime compounds, preparation method and application thereof
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Embodiment 2
[0060] Intermediate IV-1
[0061]
[0062] Add 13.9 g of intermediate III-1 to a reaction flask equipped with a stirring, condenser, and thermometer, dissolve it with 40 mL of dichloromethane, and add 17.8 g of NBS while stirring. React under light at room temperature for 6 hours (the plate layer shows that the reaction is complete). with 3 x 30mL 35% Na 2 S 2 o 3 The reaction liquid was washed with aqueous solution, and the dichloromethane layer was fully dried with anhydrous sodium sulfate, filtered, and the dichloromethane was evaporated under reduced pressure to obtain a light yellow oily product (HPLC: 97.2%). Rf = 0.35 [single site, developing solvent: v (dichloromethane): v (methanol) = 6: 1]. 1 H NMR (DMSO-d 6 , 400MHz) δ: 2.324 (s, 1H, -OH), 7.572-7.961 (m, 4H, phenyl-H).
[0063] Referring to the method of Reference Example 2, intermediates IV-2 to IV-7 can be synthesized.
[0064]
[0065]
Embodiment 1
[0067] (5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2-(4H)-onyl)-(2-chlorophenyl)methanone oxime (compound 1)
[0068]
[0069] Add 2.2g of intermediate IV-1 into a reaction flask equipped with stirring, condenser and thermometer, dissolve it with 10mL of anhydrous methanol, and add 2.76g of anhydrous potassium carbonate while stirring. 1.6 g of 5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2-(4H)-one was added to the reaction system in batches. After the addition was completed, the reaction was continued for 3.5h under reflux (the plate showed that the reaction was complete). Filter out the solid matter, evaporate anhydrous methanol to dryness, wash the reaction solution with 3×10 mL water, extract with dichloromethane, dry thoroughly with anhydrous sodium sulfate, filter, and evaporate dichloromethane under reduced pressure to obtain a black oil. Column separation [mobile phase: v (dichloromethane): v (methanol) = 9: 1], Rf = 0.45, gave a light yellow solid (HPLC: 99.3%). 1 H NMR...
Embodiment 3
[0075] (5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2-(4H)-onyl)-(2,5-dichlorophenyl)-O-ethyl ketone oxime (compound 3)
[0076]
[0077] Add 2.2 g of intermediate IV-3 to a reaction flask equipped with stirring, a condenser, and a thermometer, dissolve it with 20 mL of ethyl acetate, and add 1.0 g of sodium hydroxide while stirring. 1.6 g of 5,6,7,7a-tetrahydrothieno[3,2-c]pyridin-2-(4H)-one was added to the reaction system in batches. After the addition was completed, the reaction was continued for 8h under reflux (the plate showed that the reaction was complete). Filter off the solid matter, wash the reaction solution with 3×20 mL of water, dry it thoroughly with anhydrous sodium sulfate, filter, and evaporate the ethyl acetate under reduced pressure to obtain a yellow oil, which is separated by column [mobile phase: v (dichloromethane): v(methanol)=6:1], Rf=0.50, a white solid was obtained (HPLC: 99.8%).
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