A novel method for the preparation of N,N′-disubstituted-N′′-nitroguanidines, including a practical synthesis of the neonicotinoid insecticide clothianidin

Insecticidal and Neuroblocking Activities of Thiamethoxam-Type Compounds in the American Cockroach (Periplaneta americana L.)

“…1,2) The neonicotinoid thiamethoxam (2) may be taken as one example. This commercial insecticide shows highly effective field action especially in the control of chewing and sucking insects, common targets for imidacloprid (14), clothianidin (16) and other neonicotinoids. However it shows far less binding affinity than other neonicotinoids in housefly head membrane preparations and also in electrophysiological whole cell voltage clamp studies neurons isolated from Heliothis virescens ventral nerve cord showed no response to thiamethoxam when applied at a concentration of 0.3 mM.…”

“…Judging from its biological features and structural makeup, the diamine component of clothianidin (16), another neonicotinoid insecticide, 5) is suspected to be responsible for the actual insecticidal activity of thiamethoxam. In fact Nauen et al revealed by LC-MS/MS analysis that thiamethoxam was rapidly metabolized to clothianidin when orally administered to Spodoptera frugiperda larvae or applied to cotton plants.…”

Agrochemicals

“…Hydrolysis with hydrochloric acid finally gives the active agent. [158] Quantum mechanical calculations, NMR spectroscopic studies and X-ray analysis confirm the (E)-configuration of the C=N-NO 2 group. [137] The convergent synthesis of dinotefuran, the third-generation neonicotinoid from Mitsui Chemicals, applies a strategy analogous to clothianidin, but starts from nitroguanidine.…”

Prodrug-Oriented Molecular Design of Neonicotinoids: Preparation of Imidacloprid-Related 5,5-Dimethoxy-1,3-diazacyclohexane Derivatives and Their Insecticidal Activity

“…The mixture was stirred for 5 h at 60 C, and subsequently DMF was distilled off under reduced pressure. Preparative thin-layer chromatography on silica gel of the residue gave the product in a 37.7% yield (40 mg 17) were prepared according to the reported procedures. Reagent-grade piperonyl butoxide (PB) purchased from Tokyo Kasei Kogyo Co. (Tokyo, Japan) was used as an inhibitor of oxidative metabolism.…”