Synthesis and Herbicidal Activity of Trifluoromethyl‐Substituted Phenyl Alkyl Ketoxime Esters of Bispyribac

Abstract

A series of new trifluoromethyl-substituted phenyl alkyl ketoxime esters of Bispyribac were synthesized as potential herbicides. All synthesized compounds were characterized by nuclear magnetic resonance (NMR) spectroscopy and highresolution mass spectrometry (HRMS). Sprout method and foliar spray method were used to study the herbicidal activity of the synthesized compounds. Among all synthesized compounds, compound 3 (4-trifluoromethylphenyl n-butyl ketoxime ester of Bispyribac) exhibits the highest herbicidal activity against Echinochloa crusgalli (L.) Beauv with median effect dose (ED 50 ) of 1.7 μg/mL in pre-emergence herbicidal activity study. The structure-activity relationship analysis indicates that trifluoromethyl substitution on the phenyl group exhibits better activity than methoxy and methyl substitution on the phenyl group. The alkyl chain length also affects the activity significantly and the optimal alkyl chain length is four among the tested compounds. However, the substitution position of trifluoromethyl exhibits very limited influence on the activity. In post-emergence herbicidal activity study, compound 3 (ED 90 69.1056 g/hm 2 ) exhibits better herbicidal activity against Echinochloa crusgalli (L.) Beauv than Pyribenzoxim (ED 90 99.0810 g/hm 2 ). Moreover, compound 3 exhibits better safety to hybrid rice variety II you 084 and rice variety Nanjing 44 than Pyribenzoxim in crop safety study. Compound 3 may serve as a lead compound for future herbicide discovery.

Synthesis, Herbicidal Activity against Barnyard Grass, and Photolytic Behavior of Aryl 2,6-Dipyrimidinoxybenzoates

“…21,25,26 also exhibited good herbicidal performance. 22,23 Previously, we synthesized diaryl oxime esters of bispyribac acid bearing a pyridine moiety, exhibiting excellent herbicidal activity in greenhouse and field conditions. These compounds function as pro-herbicide activated via both enzyme-catalyzed hydrolysis and photolysis.…”

“…Methyl esterification of 2-(pyrimidin-2-yloxy)­benzoic acid minimally impacts the activity of PYB herbicides. However, when esterified with other fatty alcohols or phenol, there is a dramatic decrease in its herbicidal activity. ,,, Moreover, pyribenzoxim, an oxime esterification product of bispyribac acid, has proven successful as a light-activated herbicide, altering some characteristics of bispyribac-sodium, such as application period and safety. ,, Other oxime esters have also exhibited good herbicidal performance. , Previously, we synthesized diaryl oxime esters of bispyribac acid bearing a pyridine moiety, exhibiting excellent herbicidal activity in greenhouse and field conditions. These compounds function as pro-herbicide activated via both enzyme-catalyzed hydrolysis and photolysis .…”