77501-93-0Relevant academic research and scientific papers
Organophosphorus Antioxidants. IV. Chemical Induced Polarization of 31P Nuclei in the Reaction of Cyclic Phosphites with Hydroperoxides
Koenig, T.,Grossmann, G.,Schwetlick, K.,Rueger, C.
, p. 763 - 771 (2007/10/02)
31P-n.m.r.CIDPN is observed in the reactions of cyclic o-phenylene and ethylene phosphites with hydroperoxides.Polarized phosphorus nuclei appear especially in the phosphonate and phosphate regions.Application of Kaptein's rule shows that these products are cage or escape products of secondary or tertiary radical pairs.Solvent molecules are involved in the formation of the tertiary radical pairs.The concentration of the products formed from polarized 31P nuclei is very low.
Organophosphorus Antioxidants. III. Kinetics and Mechanism of the Decomposition of Cumyl Hydroperoxide by Cyclic Phosphites
Rueger, C.,Koenig, T.,Schwetlick, K.
, p. 622 - 632 (2007/10/02)
The reaction mechanism of cyclic esters of phosphorous acids I to VIII with cumyl hydroperoxide has been studied kinetically by means of 31P n.m.r. spectroscopy, high performance liquid chromatography and iodometric titration.The five-membered cyclic phosphites (I and II) react with cumyl hydroperoxide to give the corresponding phosphates (AI and AII) and cumyl alcohol.With more hydroperoxide or water they form the open chain phosphate esters (BI and BII) which decompose cumyl hydroperoxide catalytically giving phenol and acetone.Higher membered cyclic phosphites (III to VIII) react with cumyl hydroperoxide to give the corresponding phosphates and alcohol only.The mode of reaction depends on the hydrolysis behaviour of the cyclic phosphates (AI to AVIII).Only fivemembered cyclic phosphites which give easily hydrolyzable phosphates are able to decompose cumyl hydroperoxide catalytically.The nature of the exocyclic group in the phosphites has no influence on this behaviour.The kinetic parameters of the separate reaction steps are given.The ionic mechanism of hydroperoxide decomposition is accompanied by a homolytic one.
