Amine catalysis in phosphoryl transfer from 2,4-dinitrophenyl phosphate in aprotic and protic solvents

Reactions of tetra-n-butylammonium 2,4-dinitrophenyl hydrogen phosphate, (ArPH)^?(R₄N)⁺, in aprotic and protic solvents, in the absence and in the presence of alcohols or water, ROH, are compared with analogous reactions of the salt in the presence of hindered and unhindered amines, e.g. diisopropylethyl amine and quinuclidine. Similar studies are performed with the acid, ArPH₂, in the presence of variable amounts of amines. The release of phenol and the fate of the phosphorus compounds are followed by ¹H and ³¹P NMR spectrometry. In the absence of free unhindered amine, reactions of the monoanion are relatively slow, sensitive to steric hindrance in the alcohol, and incapable of producing t-butyl phosphate from t-butanol; reactions of the dianion are relatively fast, insensitive to steric hindrance in the alcohol, and produce t-butyl phosphate. In the presence of free unhindered amine, reactions of the monoanion are relatively fast but still sensitive to steric hindrance in the alcohol, and hence do not produce t-butyl phosphate. The intermediate CH(CH₂CH₂)₃⁺NP(O)(OH)O^? is detected in the presence of quinuclidine. Reactions of the dianion in the presence of unhindered amines are analogous to those observed in the presence of hindered amines. The uncatalyzed and the nucleophilic amine-catalyzed reactions of the monoanion are assumed to proceed via oxyphosphorane, P(5), intermediates. The dianion reactions, which are not susceptible to nucleophilic catalysis, are assumed to proceed via the monomeric metaphosphate ion intermediate, PO₃^?. Significant effects related to solvent properties are observed in these reactions.