119450-47-4Relevant academic research and scientific papers
α,α-DICHLOROALDEHYDES AND α,α-DICHLOROCARBOXYLIC ACIDS FROM LONG CHAIN 1-ALKANOLS. IMPROVED CHLORINATION IN THE SYSTEM DMF-CHCl3-MgCl2
Buyck, L. De,Casaert, F.,Lepeleire, C. De,Schamp, N.
, p. 525 - 534 (2007/10/02)
Production of α,α-dichloroaldehydes by direct chlorination of 1-alkanols with chlorine gas, catalyzed by DMF and DMF*HCl, was extended to long chain compounds (CnH2n+1OH; n = 5, 6, 8, 10, 12, 14, 16, 18).Two problems specific to the longer chains were solved to obtain isolated yields in the range 70-85 percent; a) parasitic radical chlorination was largely controlled by shielding from light; b) alkyl alkanoate side product (8 percent for n = 8 but 25 percent for n = 16 or 18) was decreased to 0-2 percent in the presence of MgCl2*H2O.Homogeneity of the reaction medium was improved with chloroform as a cosolvent.Oxidation of the aldehydes to dichlorocarboxylic acids proceeded smoothly with aqueous KMnO4 up to the tetradecanal.For the longer chains 30 percent hydrogen peroxide-NaHCO3 in acetone (overnight at 48-52 deg C) was the preferred oxidant.
