60066-33-3

Upstream product

• 4129-17-3 diphenylphosphoranyl azide 
• 67-68-5 dimethyl sulfoxide 
• 60066-32-2 trimethylammonio-P,P-diphenylphosphinamidate 
• 1499-21-4 Diphenylphosphinic chloride 
• 60066-31-1 1,1,1-trimethyl-2-diphenylphosphinoylhydrazinium iodide 
• 13703-22-5 1,1-dimethyl-2-diphenylphosphinoylhydrazine 
• 1707-03-5 diphenyl-phosphinic acid 

Relevant academic research and scientific papers

Photochemical Reactions of Trialkylammonio-N-diphenylphosphinoylimides: Rearrangement to N-Phosphinoyl Aminals and the Formation of Diphenylphosphinic Amide

The photolysis of the aminimide Ph2P(O)N--N+Me3 (1) in methanol gives the amide Ph2P(O)NH2 in high yield, but most of this is not formed from (1) directly via the nitrene; rather, it results from (solvolytic) decomposition of the phosphinoyl aminal Ph2P(O)NHCH2NMe2 (5) formed from (1) by a photochemical rearrangement.With Ph2P(O)N--N+Et3 the corresponding rearrangement product Ph2P(O)NHCHMeNEt2 (an ethylidene aminal) is not observed, but this is probably just a consequence of very rapid decomposition.Although substrates bearing both Me and Et groups on the ammonium N atom appear to form only the rearrangement product (a methylene aminal) that results form involvement of a Me group, the yield is reduced substantially relative to the yield of (5) from (1).The size of the reduction is consistent with an Et group participating in the rearrangement about twice as readily as a Me group, but the product (an ethylidene aminal) that results suffering (much) much more rapid decomposition to Ph2P(O)NH2.

DIARYLPHOSPHINIC AZIDES. PHOTOCHEMICAL REACTIONS INCLUDING REARRANGEMENT IN METHANOL

On photolysis in methanol the diarylphosphinic azides Ar2P(O)N3 (Ar=phenyl, p-tolyl, p-anisyl, p-chlorophenyl) rearrange with loss of nitrogen to form (monomeric) metaphosphonimidates which are trapped by the solvent to give methyl NP-diarylphosphonamidates (7) (41-53percent).Diarylphosphinic amides (18-42percent) are also usually formed, presumably from (triplet) nitrenes.The limited evidence available suggests that the rearrangements take place directly from the photo-excited azides rather than via (singlet) nitrene intermediates.One of the products of rearrangement, methyl NP-di(p-chlorophenyl)phosphonamidate, suffers extensive photochemical dechlorination giving methyl N-phenyl-P-p-chlorophenylphosphonamidate.