Synthesis And Insecticidal Activity Of Oxime Ether Containing An Aryl Oxazole/thiazole Ring

Inspired by the design idea of“Intermediate Derivatization Methods”,chosen the intermediates of approved agricultural chemicals as the basic skeleton,the oxime ether structure was introduced to obtain a series of novel oxime ether compounds.（1）Starting with 1-（4-chlorophenyl）-2-cyclopropylacetone,1-（4-chlorophenyl）-2-cyclopropylacetone oxime ether（A1^A9 and A17）were obtained by deuteration and etherification.1-（4-chlorophenyl）-2-cyclopropylacetone hydrazinyl oxazole methyl ether（A10^A16）were prepared by aralic acid via amidation,cyclization and etherification.1-（4-chlorophenyl）-2-cyclopropylacetone hydrazinyl thiazole methyl ether（A18^A24）were conducted by arylformamide via thio reaction,cyclization,etherification.The yield of compound A was 45.5⁸0.4%.（2）Chosen furan phenol as material,7-methoxy-2,2-dimethyl-2,3-dihydro-5-benzo-furanyl ketoxime（B1^B14）were obtained by methyl etherification,acylation,deuteration,etherification.The yield was 46.3⁷9.1%.（3）The structure of the compound A and B were confirmed by structural characterization,and the compound A12 was confirmed by X-ray single crystal diffraction.The results showed that the compound A12 belongs to the monoclinic system.The space group is P2₁/c,and each unit cell of it contains four molecules.The entire molecule has an E-type configuration centered on C（11）=N（2）.The C（3）—C（4）—C（5）plane of the benzene ring and the N（1）—C（7）—O（1）plane of the oxazole ring are connected by C（7）—C（4）,and the dihedral angle is 9.687°.The dihedral angle of C（13）—C（12）—C（17）plane and the N（2）—O（2）—C（10）plane is 87.883°.（4）The screening results of insecticidal activity at the concentration of 500 mg/L showed that the mortalities of compound A6 and A11 against Mythimna sepatara were 100%.Twelve compounds showed up to 50%inhibition rate against Aphis aphids.Five compounds’mortalities against Aphis fabae were above 70%,among them,compound A6 with the inhibition rate of 99.03%as the best one.Three compounds had more than 50%inhibition rate against Tetranychus urticae,compound A5 havig a inhibition rate of 100%as the the optimal one.