34508-68-4Relevant academic research and scientific papers
Synthesis of P-Chlorophosphaethene and N-Chloromethanimine: Estimation of Cl Substitution on the Electronic Structure of Heteroatomic Double Bonds
Lacombe, S.,Pellerin, B.,Guillemin, J. C.,Denis, J. M.,Pfister-Guillouzo, G.
, p. 5958 - 5963 (1989)
Comparison between the electronic structures of N-chloroaldimines and P-chlorophosphaethene has been achieved by photoelectron spectroscopy.Whereas N-chloroaldimines have been synthetized in the gas phase by a new "one-line" reaction starting from α-cyanoamines (vacuum gas-solid reaction, VGSR), P-chlorophosphaethene has been generated by flash vacuum thermolysis (FVT) of dichloromethylphosphine.Chlorine substitution at the heteroatom destabilizes the double bond to a much greater extent for aldimines than for phosphaethene, thus reflecting a greater interaction between chlorine and ?C=N than between chlorine and ?C=P and a more diffuse character of the ?C=P bond than the ?C=N bond.For both series the heteroatom substitution does not modify the ionization energy of the heteroatom lone pair.This observation is evidence for a counterbalance between a stabilizing inductive effect of chlorine and a destabilizing interaction betweeen the lone pairs.The discrepancy between the experimental results and the theoretical evaluation of the ionization potential is again pointed out for compounds bearing third-row atoms involved in double bonds.
Reactions of N, N-dichloroalkylamines with solid base as studied by FTIR combined with DFT calculations
Egawa,Ito,Konaka
, p. 337 - 344 (2007/10/03)
Products of vacuum gas-solid reactions of N, N-dichloroalkylamines with KOH have been identified by FTIR spectroscopy and DFT calculations. It has been found that the reactions consist of elimination of two Cl atoms accompanied with migration of an H atom, a ring carbon or a methyl group from the α-carbon to the N atom and unstable imines with a C=N double bond are formed.
