Phenolic secondary metabolites from Acorus calamus (Acorales: Acoraceae) rhizomes: the feeding deterrents for Spodoptera litura (Lepidoptera: Noctuidae).

Spodoptera litura Fabricius (Lepidoptera: Noctuidae) is one of the most destructive pests of various crops cultivated in Thailand. Spodoptera litura larvae, at early stages, attack the leaves and feed on every part of infested crops in later stages. Acorus calamus essential oil contains toxic asarones, which are generalistic cytotoxic compounds. However, the present study is the first attempt to look at safer metabolites from the rhizomes that could deter insect feeding. The objective was to use such compounds as safer residues on crops that would prevent the feeding of herbivorous lepidopterans. Accordingly, phenolic metabolites were isolated and evaluated to establish the feeding deterrence against polyphagous S. litura larvae. Methanol extract of A. calamus, chrysin, and 4-hydroxy acetophenone compounds were the most effective feeding deterrents with FD50 of 87.18, 10.33, and 70.77 µg/cm2, respectively, after 4 h of feeding on treated kale leaves in a no-choice leaf disc assay. Chrysin also reduced carboxylesterase activities (1.37-fold), whereas A. calamus methanol extract reduced glutathione-S-transferase activities (1.44-fold). Some larvae were also seen dead if they consumed the treated kale leaves. Feeding deterrent activity in the methanol extract of A. calamus was due to chrysin and 4-hydroxy acetophenone. The large-scale utilization of such compounds could help develop feeding deterrent strategies in the integrated pest management of lepidopterans.

Insecticidal and growth inhibitory effects of some thymol derivatives on the beet armyworm, Spodoptera exigua (Lepidoptera: Noctuidae) and their impact on detoxification enzymes.

BACKGROUND: Thymol is a known natural product with insecticidal activity against several insect species. A recent study on structural modifications of thymol to thymyl esters and their efficacy against Spodoptera litura suggested that such an approach could develop generalized novel insecticides/insect growth inhibitors and requires further studies to establish the efficacy against lepidopterans. RESULTS: Thymol and structurally modified eight esters were evaluated against beet armyworm, Spodoptera exigua using the topical application. Thymyl butanoate was the most toxic compound with a median lethal dose (LD50 ) of 2.33 and 1.62 µg/larva after 24 and 48 h posttreatment, respectively. All thymyl esters were potentially better than the parent compound thymol, except thymyl dibromoacetate, in their efficacy against Spodoptera exigua. Essentially, there were three levels of activity vis-à-vis the compounds used, that is, with the LD50 range of 1.5 to 5.0, 7.0 to 15.0, and > 20 µg/larva, respectively. Ovicidal activity and reduction in larval growth were also determined by treating third instars at sub-lethal doses, that is, LD50 doses of second instars. Thymyl butanoate treated larvae inhibited glutathione S-transferase, carboxylesterase, and acetylcholinesterase activities, whereas the other thymyl esters induced these enzymes. CONCLUSION: Thymyl butanoate exhibited higher toxicity against Spodoptera exigua and is the first to report about > 15.5× more toxicity than thymol and > 6.5× than thymyl cinnamate, which suggests that the efficacy was species-specific versus the chemical structural variation of the esters. © 2021 Society of Chemical Industry.

Synthesis of thymyl esters and their insecticidal activity against Spodoptera litura (Lepidoptera: Noctuidae).

BACKGROUND: Thymol, a natural phenolic monoterpene originating from Thymus vulgaris, is recognized as a safe and potent botanical insecticide to many insects. The structural modification of thymol into thymyl esters is a potential approach for the development of novel insecticides, which showed more toxicity than thymol. However, there are no reports on the insecticidal activity of thymyl esters to control Spodoptera litura. RESULTS: Thymol was structurally modified into ten thymyl esters by esterification using a new reagent, PPh3 /Br3 CSO2 Ph. The insecticidal activity of these compounds was examined against the second instars of Spodoptera litura using a topical application. Among the ten thymyl esters evaluated, thymyl cinnamate was the most toxic with LD50  = 0.41 and 0.34 µg/larva after 24 and 48 h posttreatment, respectively. In addition, thymyl cinnamate-treated larvae showed increasing carboxylesterase and acetylcholinesterase activities in vivo experiment, whereas glutathione S-transferase activity showed no significant difference. CONCLUSION: Thymyl cinnamate were first reported to exhibit toxicity against S. litura 2.41-2.46 fold more efficient than thymol. However, the detailed biochemical interactions are necessary for further development of novel insecticides. © 2019 Society of Chemical Industry.