Alcohols and phenols are phosphorylated in
high yield by reaction with various 2-chloroalkylphosphonic acids at 20-50�C in
the presence of three or more molar equivalents of cyclohexylamine or
triethylamine, the other products being the corresponding alk-1-ene and
chloride ion. The reaction probably proceeds by attack of an ROH molecule on
the phosphorus atom of a doubly-ionized phosphonate group.
2-Chlorodecyl-, 10-carboxy-2-chlorodecyl-,
and 2-chloro-octylphosphonic acid decompose rapidly in neutral solution giving
chloride ion, phosphate ion, and the corresponding alk-1-ene. In the absence of
hydroxylic compounds, 2-chlorodecylphosphonic acid is decomposed by
cyclohexylamine to dec-1-ene and a product which appears to be
N-cyclohexylphosphoramidate; t-amines and also aniline cause
dehydrohalogenation to dec-1-enylphosphonic acid.
The proton magnetic resonance spectra of
most of the phosphorus-containing substances described herein are recorded.
Acetylcholinesterase. Two types of inhibition by an organophosphorus compound: one the formation of phosphorylated enzyme and the other analogous to inhibition by substrate
