73452-25-2Relevant academic research and scientific papers
Competing sulfonylation and phosphonylation following rearrangement of an O-sulfonyl-N-phosphinoylhydroxylamine with tert-butylamine: Demonstration of a phosphonamidic-sulfonic anhydride intermediate and 18O-labelling evidence on how it may be formed
Harger, Martin J.P.
, p. 3390 - 3395 (2007/10/03)
Reaction of R(Ph)P(O)NHOSO2Bn (R = PhMeCH) with Bu tNH2 in CH2Cl2 gives a mixture of RP(O)(NHPh)NHBut and ButNHSO2Bn, the proportion of the sulfonamide increasing steadily (14.6% to 32.9%) as the concentration of amine is reduced (8.0 to 0.2 mol dm-3). Apparently the phenyl and sulfonate groups in the substrate become transposed, giving a phosphonamidic-sulfonic anhydride RP(O)(NHPh)OSO2Bn which then reacts at the phosphorus or sulfur atom to give the final products; an authentic sample of the anhydride gives similar mixtures of products. Substrate labelled with 18O in the sulfonyl position (57 mol% one 18O atom) gives sulfonamide containing most but not all of the label (43.7 mol% one 18O atom with 2.0 mol dm-3 amine). This implies partial equilibration of the three sulfonate oxygen atoms during rearrangement, or after the anhydride intermediate has been formed.
N,O-bis(diphenylphosphinoyl)hydroxylamine base-induced rearrangement to a phosphonamidic-phosphinic mixed anhydride
Harger
, p. 1451 - 1454 (2007/10/02)
The hydroxylamine derivative Ph2P(O)NHOP(O)Ph2 rearranges on treatment with Bu(t)OK-Bu(t)OH; the product contains two dissimilar P atoms (δ(p) 24.2 and 7.9, J(pp) 34 Hz) and is rapidly hydrolysed to a phosphonamidate and a phosphinate, consistent with it being the mixed anhydride Ph(PhNH)P(O)OP(O)Ph2.
O-Sulphonyl-N-phosphoylhydroxylamines: Nucleophilic Attack at Nitrogen by Dimethyl Sulphide and Allyl Methyl Sulphide Leading to N-Phosphoyl Sulphilimines
Harger, Martin J. P.,Smith, Adrian
, p. 377 - 380 (2007/10/02)
The O-sulphonyl-N-phosphoylhydroxylamines RR'P(O)NHX 6H4O; X=OMs or ONs> generally react with dimethyl sulphide and allyl methyl sulphide at room temperature in the absence of base.Nucleophilic attack at nitrogen, with displacement of the sulphonate anion, gives the protonated N-phosphoyl sulphilimines which is converted into the free sulphilimine on treatment with base.The allylic sulphilimines are labile, undergoing -sigmatropic rearrangement to N-phosphoyl-N-allylsulphenamides .In the light of these results, the formation of some sulphilimine when the base-induced rearrangement of Ph2P(O)NHOMs is carried out in dimethyl sulphide need not be seen as evidence for a nitrene mechanism.
Preparation and Characterisation of N-(Diphenylphosphinoyl)hydroxylamine, and Conversion into O-Sulphonyl Derivatives that undergo Lossen-like Rearrangement
Harger, Martin J. P.
, p. 2699 - 2704 (2007/10/02)
Having previously shown that diphenylphosphinic chloride (1a) forms O-(diphenylphosphinoyl)hydroxylamine (3a) with hydroxylamine, we have now established that N-(diphenylphosphinoyl)hydroxylamine (2a) can be obtained in good yield by reaction of (1a) with O-trimethylsilylhydroxylamine followed by methanolytic removal of the silyl blocking group.The di-p-tolyl (2b) and bis-p-methoxyphenyl (2c) analogues can be prepared in a similar way.N-(Diphenylphosphinoyl)hydroxylamine is acetylated at the O atom with acetic anhydride, and is sulphonylated at O with methanesulphonyl chloride and toluene-p-sulphonyl chloride.The N-(diphenylphosphinoyl)-O-sulphonylhydroxylamines (8) and (12a) undergo rapid and quantitative Lossen-like rearrangement with methanol-sodium methoxide to give methyl N,P-diphenylphosphonamidate (11).Comparable rearrangement are observed with t-butylamine, aniline-triethylamine, and phenol-triethylamine.
