New reaction of dithiophosphoric acids with O-thioacylhydroxylamines. Nucleophilic substitution or single electron transfer process?

On the reaction of bis(phosphothioyl)disul‐fanes with hydroxamic acids, part I: Ionic versus radical reaction pathways

“…In the previous report, we found that phosphorodithioates 4 caused the N O bond cleavage in O-thioacylohydroxyloamines [17]. Additional experiments showed that 3a did not react with phosphodithioate salts 4a at all ( 31 P NMR analysis).…”

Reaction of thio and seleno phosphoric acid derivatives with O‐thioacylated hydroxylamine

“…In the spectrum, performed after 24 h, the signal δ = 72.2 ppm, 1 J P−Se = 467.1 Hz decreased and a new one appeared at δ = 68.2 ppm, 1 J P−Se = 478.7 Hz, which we assigned to bis-(2-thiono-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl) diselenide 6e (δ = 67.2 ppm, 1 J P−Se = 471.3 Hz). Moreover, the intensity of this new signal increased after 48 and 96 h. The compound with δ = 72.2 ppm and 1 J P−Se = 467.1 Hz was isolated from the reaction mixture and was fully characterized by 1 H NMR, 13 C NMR, IR, and MS MALDI-TOF techniques. All of the above data confirmed formation of (2-thiono-5,5-dimethyl-1,3,2-dioxaphosphorinan-2-yl)-S-pivaloyl selenosulfide 4e.…”

“…The influence of radical traps and light on the reaction strongly suggests the radical mechanism of the process. Moreover, considerable ability of dithiophosphate anions to one-electron oxidation [2] implied involvement of a single electron transfer process (SET) with dithiophosphate anion 5c as a SET donor and radical scavenger as well (Scheme 2) [3].…”

Synthesis and characterization of new O,O‐diethyl phosphorothioates derived from substituted tetrazolo[1,5‐a]quinolin‐ 4‐ylmethanol derivatives

“…Phosphorodithioates have been the subject matter of several investigations involving various applications including antiviral compounds [4], plant growth regulators [5], inhibitors of number different enzymes [6], and as lubricants [7]. In recent years, a number of phosphorodithioates have been introduced as thionating agents [8,9]. Despite their wide range of pharmacological activity, industrial and synthetic applications, the synthesis of phosphorodithioates has received little attention.…”