51761-45-6Relevant articles and documents
Stereoselective synthesis and biological activities of diethyl (E)-{[4-cyano-5-[[(disubstitutedamino)methylene]amino]-3-(methylthio) -1H-pyrazol-1-yl]substituited phenylmethyl}phosphonates
Xiao, Lin-Xia,Shi, De-Qing
experimental part, p. 555 - 559 (2009/09/06)
(Chemical Equation Presented) Diethyl {[5-amino-4-cyano-3-(methylthio)-1H- pyrazol-1-yl]substitutedphenylmethyl}phosphonates 3 were efficiently synthesized via the condensation of [(1-hydrazino)substitutedphenylmethyl]phosphonates 1 with 2-[bis(methylthio
Studies of organophosphorus compounds 91: A novel synthesis of 1-hydrazinoalkylphosphonic acids and derivatives thereof
Yuan,Li
, p. 507 - 510 (2007/10/03)
Condensation of diethyl phosphite with aldehydes followed by subsequent sulfonylation of the resulting hydroxy group formed with mesyl chloride gave the corresponding 1-sulfonyloxyalkylphosphonates, which led to the convenient synthesis of 1-hydrazinoalky
Mesylate Derivatives of α-Hydroxy Phosphonates. Formation of Carbocations Adjacent to the Diethyl Phosphonate Group
Creary, Xavier,Geiger, Cristina C.,Hilton, Kathryn
, p. 2851 - 2858 (2007/10/02)
Mesylates 3-6 have been prepared and reacted in a variety of solvents.Product, rate, and solvent effect studies implicate carbocationic intermediates in these solvolyses despite the electron-withdrawing PO(OEt)2 group.Mesylate 3 gave exclusive substitution products.Optically active 3 gave racemic products on trifluoroacetolysis. α-Deuterium isotope effects were also in line with a cationic intermediate.Mesylate 4 gave some elimination product, 27, along with the substitution product 28, also via a cationic intermediate.Mesylates 5 and 6 gave exclusive elimination products.A β-deuterium isotope effect study gave a kH6/kD6 value of 2.8.This isotope effect, along with a small m value (0.45), suggested the intermediacy of a reversibly formed ion pair which subsequently loses a proton.This mechanism represents the merging of the classical E1 mechanism and the E2C(+) mechanism, the latter representing the cationic counterpart of the E1cb mechanism.Analysis of the solvolysis rates of 3 and 4 led to the conclusion that cationic intermediates are formed quite easily.Reasons are suggested for this unexpectedly facile generation of cations adjacent to the potent electron-withdrawing PO(OEt)2 substituent.