7006-95-3Relevant academic research and scientific papers
Synthesis of N,N-disubstituted phosphoramidates via a Lewis acid-catalyzed phosphorimidate rearrangement
Wilkening, Ina,Del Signore, Giuseppe,Hackenberger, Christian P. R.
supporting information; experimental part, p. 2932 - 2934 (2009/02/03)
A Lewis acid-catalyzed rearrangement of phosphorimidates allows a direct, high-yielding transformation of azides with commercially available phosphites into secondary phosphoramidates. The Royal Society of Chemistry.
A GC-MS imvestigation of the mechanism of imide-amide rearrangement
Shcherbina, T. M.,Laretina, A. P.,Gilyarov, V. A.,Kabachnik, M. I.
, p. 641 - 644 (2007/10/02)
The products of imide-amide rearrangement of trialkyl (arylamido)phosphates were studied by the GC-MS method.An ionic chain mechanism was suggested for this reaction. - Key words: capillary gas chromatography, mass spetrometry, imide-amide rearrangement, trialkyl (arylimido)phosphates, ionic chain mechanism.
GC-MS STUDY OF THE IMIDE - AMIDE REARRANGEMENT
Gilyarov, V. A.,Shcherbina, T. M.,Laretina, A. P.,Kabachnik, M. I.
, p. 1931 - 1934 (2007/10/02)
The imide - amide rearrangement of trialkyl arylimidophosphates by the action of catalytic amounts of boron trifluoride etherate proceeds at least partially by an intermolecular mechanism.Keywords: capillary gas-liquid chromatography/mass spectrometry, im
PHOSPHORYL TO CARBONYL MIGRATION OF AMINO GROUPS IN MIXED ANHYDRIDES. THE EFFECT OF N-SUBSTITUENTS
Symes, Jillian,Modro, Tomasz A.
, p. 113 - 118 (2007/10/02)
The rates of fragmentation of mixed anhydrides (MeO)(p-X-C6H4NMe)P(O)OC(O)Ph (1) (X=MeO, H, Cl, CF3) giving carboxyamides PhC(O)NMe(C6H4-X-p) were measured in CDCl3 at 70 deg C.The reaction constant ρ=+0.85 was obtained.The magnitude of ρ is taken as an indication of low sensitivity of rate to polar effects of substituents (in agreement with the concerted mechanism postulated), and its positive sign suggests that the cleavage of the P-N bond is more advanced in the transition state than is the formation of the N-C bond.
Reactions of N-Phenyl α-Halogenophosphonamidates with Alkoxide: Migration of the Anilino Group from Phosphorus to the α Carbon Atom
Harger, Martin J. P.,Williams, Andrew
, p. 1681 - 1686 (2007/10/02)
When Me2CClP(O)(NHPh)OMe is treated with 0.5M NaOMe-MeOH the anilino group migrates from phosphorus to the α carbon atom.Reaction is complete within 2 min at 60 deg C and Me2C(NHPh)P(O)(OMe)2 is formed quantitatively.Similar behaviour is observed with MeCHClP(O)(NHPh)OMe but the reaction is ca. 50-times slower and in the later stages some of the resulting MeCH(NHPh)P(O)(OMe)2 becomes demethylated.For the still less reactive compounds XCH2P(O)(NHPh)OMe (X = Cl or I) demethylation of the substrate and/or product is extensive, but with ICH2P(O)(NHPh)OEt in 0.15M NaOEt-EtOH at 60 deg C the product PhNHCH2P(O)(OEt)2 can be obtained within 1 h in high yield.The relative rates of rearrangement of the various substrates are consistent with a mechanism involving a three-membered cyclic intermediate, the phosphorus analogue of an α-lactam.
Phosphoric Amides. 5. Acid-Catalyzed Hydrolysis of Dimethyl N-(Alkylphenyl)phosphoramidates
Modro, Tomasz A.,Rijkmans, Bloys P.
, p. 3208 - 3211 (2007/10/02)
Studies of the acid-catalyzed hydrolysis of dimethyl N-(alkylphenyl)phosphoramidates demonstrate that the LFER between observed rates and basicities of the leaving amines is different for meta/para- and for ortho- substituted derivatives (slopes of logobsd vs. pKa are 0.4 and 0.9, respectively).Since the ΔS(excit) values and KSIE determined are approximately constant irrespective of the position of an alkyl group, the observed change in the slope of the rate/basicity plot is discussed in terms of the steric effects on solvation rather than as an indication of the change in reaction mechanism.
A nitrogen-15 nuclear magnetic resonance study of N-aryl phosphoramidates and phosphorimidates
Buchanan, G. W.,Morin, F. G.,Fraser, R. R.
, p. 2442 - 2446 (2007/10/02)
15N nuclear magnetic resonance chemical shifts and one-bond 15N-31P couplings are reported for a series of five N-arylphosphoramidates and four N-arylphosphorimidates.Results are interpreted in terms of an extensively delocalized N lone pair in the phosphoramidates, with p?-p? donation into the aromatic ring being dominant over p?-d? donation from nitrogen to phosphorus.
