155193-59-2Relevant academic research and scientific papers
PESTICIDAL COMPOSITIONS AND RELATED METHODS
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Paragraph 0526; 0527, (2015/04/28)
A pesticidal composition comprises at least one compounds selected from a compound of formula, or any agriculturally acceptable salt thereof, wherein R1, R2, R3, R4, R5, R6, R7,
Photolysis of olefinic N-chloropyrrolidinones, N-chlorosuccinimides and N-chloro-oxazolidinones: Reactivity of cyclic carboxamidyl, imidyl and carbamyl radicals in intramolecular reactions
Daoust, Benoit,Lessard, Jean
, p. 3495 - 3514 (2007/10/03)
N-Chloro-alkenylpyrrolidinones, an N-chloro-alkenylsuccinimide and N- chloro-alkenyloxazolidinones were prepared as precursors of olefinic cyclic carboxamidyl, imidyl and carbamyl radicals constrained to undergo intramolecular reactions uniquely via their planar or slightly twisted (30- 35°) Π(N) state (1,5-transfer of an allylic hydrogen, 5-exo or 6-exo cyclization to give bicyclo[2.2.1]azaheptane and bicyclo[3.2.1]azaoctane skeletons respectively), those intramolecular reactions being unaccessible to the planar ΣN state. Their photolysis gave products arising uniquely from intermolecular reactions of those nitrogen radicals (addition to an external olefin, hydrogen abstraction from the solvent, allylic hydrogen abstraction). An intramolecular reaction leading to bicyclo[3.3.0]azaoctane derivatives via 5-exo cyclization was observed with an N-chloro-alkenylpyrrolidinone and an N-chloro-alkenyloxazolidinone. In these two cases, both the Π(N) and the Σ(N) states of the cyclic amidyl radical allow orbital overlap for 5-exo cyclization.
Studies on the Intramolecular Cycloaddition Reaction of Mesoionics Derived from the Rhodium(II)-Catalyzed Cyclization of Diazoimides
Padwa, Albert,Hertzog, Donald L.,Nadler, William R.,Osterhout, Martin H.,Price, Alan T.
, p. 1418 - 1427 (2007/10/02)
A series of alkenyl-substituted imides were prepared by treating the appropriate amide with 2,2,6-trimethyl-4H-1,3-dioxen-4-one in xylene at 140 deg C to give the N-acetoacylated imides.Exposure of these imides to standard diazo transfer conditions gave the desired diazoimides.The carbenoid intermediate derived by treatment of the diazoimide with rhodium(II) acetate undergoes ready cyclization onto the neighboring amide carbonyl oxygen atom to generate an isomuenchnone intermediate.Subsequent 1,3-dipolar cycloaddition across the pendant olefin affords the cycloadduct in high yield.The stereochemical assignment of several of the cycloadducts was deduced by X-ray crystallography.The stereochemical outcome of the reaction is the consequence of an endo cycloaddition of the neighboring ?-bond across the transient isomuenchnone dipole.Molecular mechanics calculations were used to model energy differences between the endo and exo diastereomers.The calculations reveal that the endo diastereomers are significantly (8-12 kcal/mol) lower in energy than the corresponding exo isomers thereby providing a rationale for the preferred endo cycloaddition.Ring opening of the cycloadducts occured readily producing a transient N-acyliminium ion which either lost a proton to give an enamide or was reduced by Et3SiH to afford a bicyclic piperidine ring.
