84718-91-2Relevant academic research and scientific papers
Associative and Dissociative Mechanisms for the Rections of N-t-Butyl-P-phenylphosphonamidic Chloride with Isopropylamine and t-Butylamine: Competitive, Kinetic, and Stereochemical Studies
Freeman, Sally,Harger, Martin J. P.
, p. 81 - 90 (2007/10/02)
The substitution reactions of N-t-butyl-P-phenylphosphonamidic chloride (4a) with isopropylamine and t-butylamine (or t-pentylamine in stereochemical experiments) in MeCN at 0 deg C can apparently proceed by one associative and two dissociative mechanisms
Photolysis of Diphenyl- and t-Butyl(phenyl)-phosphinic Azides: Dimethyl Sulphide as a Nitrene Trap, and Its Influence on the Curtius-like Rearrangement
Harger, Martin J.P.,Westlake, Sally
, p. 2351 - 2356 (2007/10/02)
Photolysis of Ph2P(O)N3 in benzene containing MeOH gives a high yield (72percent) of the phosphonamidate PhP(O)(OMe)NHPh (3) resulting from Curtius-like rearrangement.When some of the benzene solvent is replaced by Me2S the yield of the rearrangement prod
DIMETHYLSULPHIDE AS A NITRENE TRAP IN THE PHOTOLYSIS OF SOME PHOSPHINIC AZIDES
Harger, Martin J. P.,Westlake, Sally
, p. 3621 - 3622 (2007/10/02)
When PhRP(O)N3 (R=Ph or t-Bu) is photolysed in dimethylsulphide substantial amounts (22-32percent) of PhRP(O)N:SMe2 and PhRP(O)NHCH2SMe are produced and rearrangement is less important than in benzene.
PHOTOLYSIS OF SOME UNSYMMETRICAL PHOSPHINIC AZIDES IN METHANOL. RELATIVE MIGRATORY APTITUDES OF ALKYL GROUPS AND PHENYL IN THE CURTIUS-LIKE REARRANGEMENT.
Harger, Martin J. P.,Westlake, Sally
, p. 3073 - 3078 (2007/10/02)
When an alkylphenylphosphinic azide RPhP(O)N3 (R=Me, Et, Pri or But) is photolysed in MeOH either the alkyl or phenyl group can migrate from P to N in the Curtius-like rearrangement.The composition of the product shows that migration of the alkyl group R is preferred.However, the preference is not great and decreases as R changes But->Pri->Et->Me-> (approx. migratory aptitudes relative to Ph: 2.1, 1.7, 1.3, 1.2 respectively), probably because the Ph-P bond is better able to assume the correct conformation for Ph migration when R is less bulky.For t-butylmethylphosphinic azide there is very little preference for migration of But relative to Me.Small amounts of unrearranged products such as ButPhP(O)NHOMe and ButPhP(O)NH2 are generally produced in the photolyses, together with the methyl phosphinates RPhP(O)OMe (major product when R=Me) resulting from (non-photochemical) solvolysis of the azide.
