TY - JOUR
T1 - Aminolysis and base-catalysed hydrolysis of aryl phenylphosphonamidates and amidothionates
T2 - Reactions close to the E1cB-bimolecular nucleophilic mechanistic borderline
AU - Williams, Andrew
AU - Douglas, Kenneth T.
AU - Loran, John S.
PY - 1975
Y1 - 1975
N2 - Trapping experiments with amine nucleophiles of high negative Brønsted-type exponent confirm that O-aryl NP-diphenylphosphonamidates [PhPO(NPh)OAr] release phenolate in base via an E1cB process. The corresponding phosphonamidothionates, however, hydrolyse in base via an addition-elimination pathway. These conclusions are consistent with the poorer electron-donating power of the thioanion (P-S-) compared with oxyanion (P-O-) to expel phenolate from the corresponding conjugate base [PhPS(N̄Ph)OAr].
AB - Trapping experiments with amine nucleophiles of high negative Brønsted-type exponent confirm that O-aryl NP-diphenylphosphonamidates [PhPO(NPh)OAr] release phenolate in base via an E1cB process. The corresponding phosphonamidothionates, however, hydrolyse in base via an addition-elimination pathway. These conclusions are consistent with the poorer electron-donating power of the thioanion (P-S-) compared with oxyanion (P-O-) to expel phenolate from the corresponding conjugate base [PhPS(N̄Ph)OAr].
UR - http://www.scopus.com/inward/record.url?scp=37049130460&partnerID=8YFLogxK
U2 - 10.1039/P29750001010
DO - 10.1039/P29750001010
M3 - Article
AN - SCOPUS:37049130460
SN - 1472-779X
SP - 1010
EP - 1016
JO - Journal of the Chemical Society, Perkin Transactions 2
JF - Journal of the Chemical Society, Perkin Transactions 2
IS - 10
ER -