Novel Anthranilic Diamide Insecticides: Design, Synthesis, and Insecticidal Evaluation

Abstract

Three series of new anthranilic diamide derivatives containing sulfide, N-cyanomethylsulfilimine, and N-cyanomethylsulfoximine groups were designed and synthesized by coupling the active substructures of anthranilic diamides and sulfoxaflor. The structures of the synthesized compounds were confirmed by infrared spectroscopy, 1 H and 13 C NMR, and elemental analysis. Several unique structural characteristics were revealed via the crystal structure analysis of compoundBioassay results indicated that most of the synthesized compounds showed superior insecticidal activities against Mythimna separata and Plutella xylostella when compared with the positive control cyantraniliprole. In particular, N- (2-(2-methyl-2-(N-cyanomethylsulfideimino)propylcarbamoyl)-4-chloro-6-methylphenyl)-3-bromo-1-(3-chloropyridin-2-yl)-1H-pyrazole-5-carboxamide 17e showed excellent insecticidal activity against Mythimna separata, with a mortality rate of 100 % at a concentration of 1 mg mL À1 . These results indicated that sulfide, N-cyanomethylsulfilimine, and N-cyanomethylsulfoximine moieties, as important active substructures, could improve or maintain the activity of the anthranilic diamide and promote novel pesticide development.

Synthesis, Physicochemical Properties, and Biological Activities of 4-(S-Methyl-N-(2,2,2-Trifluoroacetyl)Sulfilimidoyl) Anthranilic Diamide

“…The nitrated product 9 was readily converted to thiomethylated aniline 11 by reaction sequence previously used [31,33,34]. Then, 2-amino-3-methyl-5-(methylthio)benzoic acid 11 was coupled with 3-bromo-1-(3-chloropyridin-2-yl)-1 H -pyrazole-5-carboxylic acid 13 [12,14,33,34] to give the desired benzoxazinone 12 in good yield [13]. After ring opening reaction of 12 with methylamine [12,14,29,30,34], 4-methylthio anthranilamide 14 was readily obtained.…”

“…Examples of alkyl sulfilimine- and sulfoximine-substituted insecticides [1,2,3,4,5,6,7,8,9,10,11,12,13,14,15]. …”

“…Consequently, a large number of studies have examined the chemistry and mode of action of sulfoxaflor and sulfoximine insecticides [4,5,6,7,8]. As shown in Figure 1, the interest in the sulfoximine moiety has led to the discovery of highly-active sulfilimine-containing insecticides 1 – 4 [9,10,11,12,13]. For patent applications, researchers at BASF prepared sulfilimine-based anthranilic diamides 4 and reported that it is highly active in insects which are resistant to ryanodine modulator insecticide [13].…”

Copper‐Catalyzed Direct Sulfoximination of Heteroaromatic N‐Oxides by Dual C−H/N−H Dehydrogenative Cross‐Coupling

“…[1] The unique properties make sulfoximinesa ttractive for life science projects directedt owards medicinal and crop protection applications. [2,3] Therefore, sulfoximines have been introduced as antibiotics, antithrombotics, and tumor metastasis inhibitors. [2] In the contexto ft his study,i ti sn oteworthy that various N-(hetero)arylsulfoximines showeda nticancer activity [4] and that some derivatives with this N-substitution pattern proved applicable as agrochemicals.…”

The Study of Novel Sulfilimines as Potential Insects Modulators

“…Especially compound D (Figure 1) displayed 100% larvicidal activities at 0.25 mg/l , which reached the same larvicidal level as Flubendiamide. Later, Fan et al [13] reported that anthranilic diamides structures containing N-cyano sulfiliminyl moieties also could maintain the activity. The results prompted us to look for new structures with better insecticidal potency by structure optimization.…”