Podophyllotoxin is isolated as a sustainable natural bioresource from the roots and rhizomes of Podophyllum hexandrum and Juniperus Sabina . In continuation of our program aimed at the discovery of biorenewable natural product-based pesticides, a series of 4α-acyloxy derivatives of 2'-chloro-5-bromopicropodophyllotoxin or 2',5-dibromopicropodophyllotoxin were synthesized by structural modification of podophyllotoxin, and evaluated as insecticidal and acaricidal agents against two serious agricultural pests, Mythimna separata Walker and Tetranychus cinnabarinus Boisduval. Among all derivatives, compounds 6a and 7a exhibited more promising insecticidal and acaricidal activities than podophyllotoxin, and the final mortality rates of 6a , 7a and 1 against M. separata (at 1 mg/mL) and T. cinnabarinus (at 0.5 mg/mL) were 50%/53.3%/36.7%, and 33%/41.8%/1.6%, respectively. This suggested that introduction of the acetoxy moiety at the C-4 position of 2'-chloro-5-bromopicropodophyllotoxin/2',5-dibromopicropodophyllotoxin was necessary for the insecticidal and acaricidal activities.
To discover new natural-product-based potential pesticides, 85 matrinic acid/alcohol/ester derivatives were synthesized by structural modifications of a quinolizidine alkaloid matrine. N-(4-Methyl)benzylmatrinyl n-decylate (76) and N-(2-chloro)benzylmatrinyl n-undecylate (86) exhibited greater than seven-fold more pronounced acaricidal activity than matrine against Tetranychus cinnabarinus; N-(2-chloro)benzylmatrinyl benzoate (80) showed the most promising insecticidal activity against Mythimna separata. The carboxyl group of matrinic acids and introduction of n-decyl/n-undecylcarbonyl into matrinic alcohols were important for the acaricidal activity; introduction of alkyloxy into the carboxyl of matrinic acids and introduction of the electron-withdrawing groups on the N-benzyl of matrinic esters were necessary for the insecticidal activity. Through RT-PCR and qRT-PCR analysis, it was shown that the lactam ring of matrine was vital for action on VGSC; opening the lactam ring of matrine and the alkylcarbonyl of side-chain were two important factors for acting with α1, α2, and α4 nAChR subunits; α1, α2, α4, and β3 subunits may be the target of action of compound 86 against T. cinnabarinus.
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