3719-53-7Relevant articles and documents
Radical and Ionic Reactions of (Benzoylmethyl)mercurials
Russell, Glen A.,Kulkarni, Shekhar V.,Khanna, Rajive K.
, p. 1080 - 1086 (2007/10/02)
Photolysis of PhCOCH2HgCl or (PhCOCH2)2Hg yields benzoylmethyl radicals which can be trapped by anions such as Me2C=NO2-, RC(CO2Et)2-, RC(O-)=CH2 or by other electron-rich systems such as (RO)3P, N-methylpyrrole, enamines, or norbornene.Electron transfer from the adduct radicals to the mercurials yields PhCOCH2A from the anions A-, PhCOCH2P(O)(OR)2 from P(OR)3, and the phenacyl derivative from N-methylpyrrole or enamines.Easily oxidized anions such as PhCOCPh2- or PhC(CH3)=NO2- react with PhCOCH2* by electron transfer to yield the dimer derived from the anion.Addition of PhCOCH2* to norbornene yields a substituted 3-benzoylpropyl radical which cyclizes at the ortho position of the benzoyl group to give the α-tetralone derivative.
Reaction of 2-Chlorooxiranes with Phosphites and Phosphanes: A New Route to β-Carbonylphosphonic Esters and -phosphonium Salts
Herzig, Christian,Gasteiger, Johann
, p. 601 - 614 (2007/10/02)
Reaction of alkylsubstituted 2-chlorooxiranes 6 with trialkyl phosphites 11 gives β-carbonylphosphonic diesters (12a, b, 15a, b, 20a, 21a), free of isomeric enol phosphates or α,β-epoxyphosphonates. 2-Chloro-2-(chloromethyl)oxirane (6c) undergoes with 11 an Arbusov reaction followed by a Perkow reaction ( -> 18 -> 17).The limitation of the method is probed with sterically crowded substituents in 3-position of 6. 6b yields with triphenylphosphane a β-ketophosphonium salt (23), which can be converted to a keto-ylide (24).
