Reaction of Diphenyldiazomethane with Phosphorus Monothioacids

The mechanism of the reaction of phosphorus monothioacids with diaryldiazomethanes was studied in different solvent systems at 20 °c. The thiolo to thiono product ratios were determined by 1H NMR spectroscopy and g.l.c. of the reaction mixtures. The results imply that the reaction involves two competing processes leading to the corresponding S- and 0-isomeric esters

3-Aryl(hetaryl)-3-hydroxy-2-phosphorus-substituted acrylonitriles. Synthesis and experimental and theoretical conformational analysis

Under conditions of the phase transfer catalysis, acylation of (thio)phosphorylacetonitriles by (het)aroyl chlorides affords the Z-enol forms of C-acylation products in high yields. Their configurations were studied by IR spectroscopy, dipole moment measurements, and ab initio quantum-chemical calculations [B3LYP/6-31G(d)]. The C=C double bond and the phosphoryl or thiophosphoryl group have an s-cis arrangement. The possibility of strong intramolecular hydrogen bonding in these conformers is the governing factor responsible for the three-dimensional structures of the compounds under investigation. Derivatives of nicotinic acid existing in the individual form as zwitterions are the only exceptions