Construction, Pesticidal Activities, Control Effects, and Detoxification Enzyme Activities of Osthole Ester/Amide Derivatives

Abstract

Pesticide research and development has entered an era of safety, efficiency, and environmental friendliness. Discovery of effective active products directly or indirectly from plant secondary metabolites as pesticide candidates has been one of the current research focuses. Herein, two series of new ester and amide derivatives were prepared by structural modifications of a natural coumarin-type product osthole at its C-4′ position. Their structures were characterized by IR, mp, 1H NMR, and HRMS. Confirmation of steric configuration of seven compounds was based on single-crystal analysis. Against Tetranychus cinnabarinus Boisduval (Acari: Tetranychidae), (2′E)-3′-ethoxycarbonylosthole (4b) and (2′E)-3′-(n)­hexyloxycarbonylosthole (4e) exhibited 3.2 and 3.1 times acaricidal activity of osthole, and particularly, they also showed 2.4 and 2.2 times control efficiency on the 5th day of osthole. Against Aphis citricola Van der Goot (Homoptera: Aphididae), (2′E)-3′-(p-CF3)­benzyloxycarbonylosthole (4w), (2′E)-3′-benzylaminocarbonylosthole (5f), and (2′E)-3′-phenylethylaminocarbonylosthole (5g) showed 1.9–2.1-fold aphicidal activity of osthole. Furthermore, the changes in two detoxification enzyme [carboxylesterase (CarE) and glutathione S-transferase (GST)] activities over time in treated T. cinnabarinus were investigated. These results can pave the foundation for future design and preparation of osthole derivatives as botanical agrochemicals.

High Value-Added Application of Natural Plant Products in Crop Protection: Construction and Pesticidal Activities of Piperine-Type Ester Derivatives and Their Toxicology Study

“…The control efficiency of compounds 1 and 4f against T. cinnabarinus was evaluated in the greenhouse. , …”

“…The acaricidal activity of compounds 1 – 3 , 4a – z , and 4a′ – c′ against T. cinnabarinus was evaluated by the slide-dipping method. , …”

“…Piperine ( 1 , Figure ) as a natural alkaloid isolated from the black pepper (Piper nigrum), exhibited a variety of biological properties including anticancer, , anti-inflammation, anti-Alzheimer’s disease (AD), anti-Parkinson’s disease (PD), , antiseizure, antiadipogenic, and insecticidal activities. − Previously, we found that the ester group can play a key role for improving agrochemical activities, for instance, some of osthole esters ( I and II , Figure ), , andrographolide esters ( III , Figure ), and limonin esters ( IV , Figure ) showed interesting pesticidal activities. In addition, the Vilsmeier–Haack–Arnold (VHA) reaction has frequently been used in the total synthesis of natural products and drugs, and its main function includes aromatic formylation reaction or as a fulcrum for the introduction of different functional groups to obtain target compounds, such as homofascaplysin C and commercial anticarcinogen Sunitinib malate. , Consequently, in this paper we wanted to prepare a series of new piperine-type ester derivatives via the key intermediate aldehyde by application of a VHA formylation reaction of piperine (Figure ).…”

Synthesis of Piperine-Based Ester Derivatives with Diverse Aromatic Rings and Their Agricultural Bioactivities against Tetranychus cinnabarinus Boisduval, Aphis citricola Van der Goot, and Eriosoma lanigerum Hausmann

“…Then, in the presence of NaBH 4 and MeOH, compound 2 was reduced to give compound 3 [ 45 ]. Finally, in the presence of EDCI and DMAP, target compounds 4–12 were obtained by reaction of compound 3 with aromatic acids RCO 2 H in 44–57% yields [ 46 , 47 ]. The chemical structures of compounds 2–12 were all determined by mp, IR, 1 H NMR, and 13 C NMR.…”

“…Particularly, compounds 9 and 11 were 45.4– and 47.6–fold stronger than piperine. Notably, their acaricidal activities were more potent than those of 7-oxycarbonylandrographolide, cholesterol, and osthole ester/amide derivatives [ 38 , 41 , 45 , 46 ]. When compared with our previous results [ 48 ], it suggested that introduction of the CH 2 between the phenyl/4-Fphenyl/4-Clphenyl and the carbonyl groups was very important for the acaricidal activity.…”