N-NITROSAMINES AS REAGENTS FOR THE =C=S=C=O TRANSFORMATION

Article abstract of DOI:10.1016/S0040-4020(01)88548-3

N-nitrosopiperidine and N-nitroso-N-methylaniline react in acidic solution with thiocarbonyl compounds to give the corresponding carbonyl analogues.Secondary- and tertiary thioamides, xanthione, thio- and dithiobutyrolactone, thiocoumarin, certain thiourea derivatives, dithio-O,O-thiocarbonic, S,S-trithiocarbonic- and N,N disubstituted thiocarbamic esters are all converted into the corresponding O-analogues.Thiobenzamide and N-phenylthiourea yield 1,2,4-thiadiazoles.All the reactions are run with iodide (I^-) as NO⁺-carrier.The kinetics of the reaction have been studied under pseudo-first order conditions, and the reaction rate is proportional to the Pearson's nucleophilicity parameter of ions.The =C=S <*> =C=O transformation is also found to take place in gastric juice.