Reaction of 2-diethylamino-3-diethylaminomethyl-1,3,2-benzoxazaphospholine with hydroxyl-containing compounds

Amides of Trivalent Phosphorus Acids as Phosphorylating Reagents for Proton-Donating Nucleophiles

“…Let us consider the influence of structural factors on the route of alcoholysis and phenolysis of ring systems whose molecules contain both exo-and endophosphamide bonds. Data on the reactions of alcohols and phenols with equimolar amounts of 2-alkylamino-1,3,2-oxazaphospholanes and -diazaphospholanes 11,[148][149][150] and phosphorinanes [150][151][152][153] can be found in the literature. These reactions mainly result in the cleavage of exocyclic bonds.…”

“…Some competitive relationships have been elucidated; for example, it was shown that on treatment with benzenethiol, N-aminomethylated phosphamides are first deaminomethylated and only after completion of this process phosphorylation occurs (Scheme 132). 629 Note that the above-mentioned aminomethylated phosphamide reacts with alcohols only with cleavage of the phosphamide bond. 9 Mercaptans are also phosphorylated by phosphimides; when equimolar amounts of reactants are taken, only the π-bond of the phosphimine function is cleaved.…”

“…630 The reactions of ATPA with aromatic thiols usually lead to good results. 629,631 The use of aliphatic thiols is not always fruitful because their desulfuruzation occurs in parallel. 631 This trouble can be eliminated by using acid catalysis, which, in addition, permits phosphorylation to be carried out under milder conditions.…”