170303-71-6Relevant academic research and scientific papers
Biomimetic building-up of the carbamic moiety: The intermediacy of carboxyphosphate analogues in the synthesis of N-aryl carbamate esters from arylamines and organic carbonates promoted by phosphorus acids
Aresta, Michele,Berloco, Chlara,Quaranta, Eugenio
, p. 8073 - 8088 (1995)
The reaction of aromatic amines with dimethyl carbonate (DMC) or diphenyl carbonate (DPC) in the presence of organo-phosphorus acids [Ph2P(O)OH (1); (PhO)2P(O)OH (2); (BuO)2P(O)OH/(BuO)P(O)(OH)2 equimolar mixture (3)] affords carbamate esters, ArNHC(O)OR (R = Me, Ph) with high selectivity. The catalytic role played by the P-acid has been investigated and rationalized in terms of a reaction mechanism involving the intermediate formation of a carbonic-phosphinic(phosphoric) anhydride X2P(O)OC(O)OR (X = Ph, PhO; R = Me, Ph). The proposed mechanism shows intriguing analogies with the mechanism of formation of carbamate anion in living systems by carbamoyl phosphate synthetase (CPS) enzyme. Copyright
Mixed anhydrides: Key intermediates in carbamates forming processes of industrial interest
Aresta, Michele,Dibenedetto, Angela
, p. 685 - 690 (2007/10/03)
Mixed anhydrides of carbonic acid with phosphonic or carbamic acid, are mimic of relevant biological systems, and behave as key intermediates in transesterification processes that afford carbamates of industrial interest. They are formed in the phosphonic acids mediated or direct transesterification reaction of organic carbonates with amines to afford carbamates and have been isolated and characterised in the solid state and solution. Their conversion into the products has been demonstrated to occur with high regioselectivity. The application of such intermediates in some synthetic processes is discussed.
