1, 2, 4-triazole Schiff base thioether derivative and preparation method and application thereof
A technology of Schiff base sulfides and derivatives, applied in botany equipment and methods, chemicals for biological control, biocides, etc., can solve the problem of increasing the risk of pest resistance, increasing the amount of use, Reduced efficacy of herbicides, etc.
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Embodiment 1
[0029] Embodiment 1: the preparation method of compound 2:
[0030] In a 50 ml single-necked round-bottomed flask, add 0.60 mL of 80% hydrazine hydrate solution and 0.0041 mol of aromatic (hetero)cyclic carboxylate 1 successively, and described aromatic (hetero)cyclic carboxylate methyl is selected from: 2-pyridine carboxylate , Methyl thiophene-3-carboxylate, heat the system to reflux, monitor the reaction process with TCL, stop the reaction after about 5 hours of reaction, cool the system to room temperature, add a small amount of absolute ethanol to the reaction solution, and rotary evaporate under reduced pressure The excess hydrazine hydrate was removed, and the residual solid was recrystallized in absolute ethanol to obtain a white solid, which was dried in a vacuum oven, which was aromatic heterocyclic hydrazide 2, with a yield of 85-90%; when R 1 When it is 3-thienyl, the NMR data are as follows:1 HNMR (CD 3 OD,400MHz): δ8.02-8.01(m,1H),7.48-7.47(m,2H). The amount of...
Embodiment 2
[0031] Embodiment 2: the preparation method of compound 3:
[0032] In (0.46g, 0.0082mol) KOH solution in absolute ethanol, add 0.0041mol aromatic (hetero)cyclic hydrazide 2, and add (0.74mL, 0.0123mol) CS 2 Solution, heating up to reflux, TCL monitors the reaction process, after the reaction is over, the solvent is evaporated under reduced pressure, the crude product is the potassium salt of aromatic (hetero) ring-3-oxadiazole mercapto, and this potassium salt is dissolved in 3mL80% hydrazine hydrate Continue the reflux reaction in the solution for about 4 hours, then pour the reaction solution into 200mL ice water to dissolve, use 10% HCl to adjust the pH of the solution to about 5, a yellow precipitate is formed, filter under reduced pressure, and dry overnight in a vacuum oven to obtain 4- Amino-5-mercapto-1,2,4-triazole compound 3, yield 70-82%; when R 1 When it is 3-thienyl, the NMR data are as follows: 1 H NMR (CD 3 Cl, 400MHz): δ8.22 (d, J = 2.0Hz, 1H), 7.44-7.39 (m...
Embodiment 3
[0033] Embodiment 3: the preparation method of compound 4:
[0034] In a dry 50mL round bottom flask, add successively 0.0025mol compound 3, 5mL absolute ethanol solvent, 1.05mL triethylamine, 0.0030mol bromomethyl aryl (hetero) ring derivative, the bromomethyl aryl (hetero) ) ring derivatives are selected from: 1-bromomethyl-2,4-dichlorobenzene, 2-bromomethylpyridine, 4-bromomethyl-3,5-dimethylisoxazole, 3-chloromethyl -1,2,4-Triazolin-5-one, bromomethylcyclopropane, heated to reflux, TLC to monitor the reaction process, after the reaction, the solvent was evaporated under reduced pressure, and the crude product was dissolved in 80mL of dichloromethane , washed with 50mL saturated brine, extracted and separated, dried the organic layer with anhydrous sodium sulfate, filtered with suction, and evaporated the solvent under reduced pressure. The crude product was purified by 200-300 mesh silica gel column chromatography to obtain 1,2,4-triazole amino derivative Matter 4, eluent...
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