42399-89-3Relevant articles and documents
HYDROXYLAMINE AS AN AMBIDENT NUCLEOPHILE. REACTION WITH PHORONE
Ly, Bunkoy,Petrus, Francoise,Verducci, Jean,Gombeau, Danielle,Pfister-Guillouzo, Genevieve
, p. 279 - 284 (2007/10/02)
The reaction of hydroxylamine with phorone is described and the results compared with those previously reported for the reaction with mesityl oxide.The hydroxylamine acts as an ambident nucleophile; when liberated from its hydrochloride, without an excess of base, it undergoes 1,4-addition to phorone via the nitrogen atom.Under basic conditions 1,4-addition is observed solely through the oxygen atom, thereby producing a non-isolable ethylenic oxiamino ketone intermediate, which in turn reacts to give up to five different products depending on the experimental conditions.The results are rationalised with the aid of perturbation energy calculations which show that, unlike mesityl oxide, the C(4) of phorone can give energetically favourable interactions only with very soft nucleophiles, such as NH2O(-).In contrast, the absence of 1,2-attack cannot be interpreted in terms of the electronic properties of the molecule, the absence of reaction of the carbonyl group being explained by its high steric crowding.