29574-16-1Relevant articles and documents
Synthesis and Properties of Mixed Substituted (Chloroacetyl)organylphenylphosphanes
Lindner, Ekkehard,Merkle, Ralf Dieter,Mayer, Hermann August
, p. 645 - 658 (2007/10/02)
The mono-, di- and trichloroacetylorganylphenylphosphanes X1X2CClC(O)PPhR (3av-cz) are obtained by reaction of Me3SiPPhR (2v-z) with the azid chlorides X1X2CClC(O)Cl (1a-c).Increasing content of chlorine results in a shift of the >C=O band and the 31P signal to higher wavelengths and fields, respectively, in the IR and 31P NMR spectra of 3av-cz.Due to the centre of chirality at the phosphorus atom in the 1H NMR spectra one observes diastereotopic protons in the chloroacetyl moiety of 3av-az and of the P-adjacent CH2 protons of 3aw-cw and 3ay-cy.The magnetic inequivalence of both methyl substituents in the isopropyl groups of 3ax-cx is observable also in the 13C and 1H NMR spectra.Because of steric reasons the free rotation about the P-isopropyl axis is hindered up to 355 K.From the coalescence temperature the free activation energy ΔG* is calculated to give 74.7 kJ/mole.The degradation of the thermolabile compounds 3av-cz results in the formation of the chlorophosphanes 5v-z.Individual investigations on 3bv, 3bw and 3by indicate the formation of mono- and dichloroacetyl chloride.The appearance of ClCH2C(O)Cl proceeds via the chloroketene 4b.
