Synthesis of Novel Oxime Sulfonate Derivatives of 2'(2',6')-(Di)chloropicropodophyllotoxins as Insecticidal Agents.
To discover novel natural-product-based pesticidal agents, we prepared a series of oxime sulfonate derivatives of 2'(2',6')-(Di)chloropicropodophyllotoxins by structural modification of podophyllotoxin. Their structures were well-characterized by proton nuclear magnetic resonance ((1)H NMR), high-resolution mass spectrometry (HRMS), optical rotation, and melting point. Moreover, the key steric structure of compound 5f was unambiguously determined by single-crystal X-ray diffraction. Additionally, their insecticidal activity was evaluated at 1 mg/mL against the pre-third-instar larvae of oriental armyworm (Mythimna separata Walker), a typical lepidopteran pest. Among all derivatives, compounds 4c, 5c, and 5d exhibited more promising insecticidal activity, with the final mortality rates greater than 60%, when compared to their precursor podophyllotoxin and the positive control, toosendanin. It demonstrated that introduction of the chlorine atom at the C-2' or C-2',6' position on the E ring of picropodophyllotoxin or oxime sulfonate derivatives of picropodophyllotoxin was important for the insecticidal activity and introduction of a halogen (e.g., fluorine, chlorine, or bromine) atom-substituted phenylsulfonyl group on the oxime fragment of 2'(2',6')-(di)chloropicropodophyllones could lead to more promising compounds.
['Wang|Rong|R|', 'Zhi|Xiaoyan|X|', 'Li|Jie|J|', 'Xu|Hui|H|']
D000818:Animals D007306:Insecticides D007814:Larva D009682:Magnetic Resonance Spectroscopy D015394:Molecular Structure D009036:Moths D010091:Oximes D011034:Podophyllotoxin
oxime sulfonate structural modification podophyllotoxin insecticidal activity Mythimna separata Walker natural-product-based insecticide