Design, Synthesis, Crystal Structure Analysis, and Insecticidal Evaluation of Phenylazoneonicotinoids

• Published in: Journal of agricultural and food chemistry Vol. 59; no. 19; pp. 10615 - 10623
• Main Authors: Ye, Zhenjun, Xia, Shuang, Shao, Xusheng, Cheng, Jiagao, Xu, Xiaoyong, Xu, Zhiping, Li, Zhong, Qian, Xuhong
• Format: Journal Article
• Language: English
• Published: WASHINGTON American Chemical Society 12.10.2011; Amer Chemical Soc
• Subjects: acetylcholine; Agriculture; Agriculture, Multidisciplinary; Anabasine - analogs & derivatives; Anabasine - chemical synthesis; Anabasine - chemistry; Animals; Aphids; Aphis craccivora; Azo Compounds - chemical synthesis; Azo Compounds - chemistry; Biological and medical sciences; Chemistry; Chemistry, Applied; cowpeas; Crop and Animal Protection Chemistry; crystal structure; Crystallization; Food industries; Food Science & Technology; Fundamental and applied biological sciences. Psychology; imidacloprid; Insecta - chemistry; insecticidal properties; Insecticides - chemical synthesis; Insecticides - chemistry; insects; Life Sciences & Biomedicine; Models, Molecular; nuclear magnetic resonance spectroscopy; Physical Sciences; Receptors, Nicotinic; Science & Technology; Structure-Activity Relationship; X-radiation; insecticide; phenylazo compounds; π−π stacking; neonicotinoids; PI INTERACTION; ANALOGS; ACHBP; HETEROCYCLIC KETENE AMINALS; NICOTINIC RECEPTOR; ELECTRONEGATIVE PHARMACOPHORE; pi-pi stacking; DERIVATIVES; Design; Evaluation; Insecticide; Synthesis; Pesticides; π―π stacking; Crystalline structure
• DOI: 10.1021/jf2029708
• ISSN: 0021-8561

On the basis of research of the proposed modes of action between neonicotinoids and insect nicotinic acetylcholine receptor (nAChR), a series of phenylazoneonicotinoids were designed and synthesized to further promote the π–π interaction between molecule and amino acid residues. The target compounds have been identified on the basis of satisfactory analytical and spectral (1H NMR, 13C NMR, HRMS, and X-ray) data. The preliminary results revealed that tiny differences in substitutes resulted in different configurations and great bioactivity variations. Some compounds with electron-donating groups on positions 2 and 6 of the phenyl ring presented higher insecticidal activity than imidacloprid against cowpea aphids (Aphis craccivora). The impressive crystal structure of the excellent insecticidal activity compound 9q clearly proved that the functional electronegative pharmacophore was approximately vertical to the methyleneimidazolidine plane. The differences in the mode of interaction on nAChR of typical compounds 9h and 9q remain unclear.