79238-46-3Relevant academic research and scientific papers
Some Rearrangements of Unsaturated Phosphonate Esters
Cooper, Dianne,Trippett, Stuart
, p. 2127 - 2133 (2007/10/02)
α-Hydroxyalk-2-enylphosphonates undergo Claisen orthoester rearrangement on heating with orthoesters, and their arylsulphenates undergo -sigmatropic rearrangement to give 3-arylsulphinylalk-1-enylphosphonates.The addition of allyloxide anion to the central carbon of the allene Me2C=C=CHP(O)(OEt)2 is followed by rapid Claisen rearrangement of the resulting allylic carbanion to give the two possible β-ketoalkylphosphonates.Allenic phosphonates of the general formula R1R2C=CHnCR3=C=CHP(O)(OEt)2 have been prepared: when R1 = R2 = H, R3 = Me, and n = 2, Cope rearrangement occurs to give isomeric dienes; when R1,R2,R3 = Me and n = 0, hydride shift gives a triene which then cyclises to a cyclohexadiene; when R1 = Me, R2 = H, R3 = H or Me, and n = 0, the diene component can be used in Diels-Alder reactions.
