BIOMIMETIC BUILDING-UP OF THE CARBAMIC MOIETY - THE INTERMEDIACY OF CARBOXYPHOSPHATE ANALOGS IN THE SYNTHESIS OF N-ARYL CARBAMATE ESTERS FROM ARYLAMINES AND ORGANIC CARBONATES PROMOTED BY PHOSPHORUS-ACIDS | Health & Environmental Research Online (HERO)

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Citation
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HERO ID

7440922

Reference Type

Journal Article

Title

BIOMIMETIC BUILDING-UP OF THE CARBAMIC MOIETY - THE INTERMEDIACY OF CARBOXYPHOSPHATE ANALOGS IN THE SYNTHESIS OF N-ARYL CARBAMATE ESTERS FROM ARYLAMINES AND ORGANIC CARBONATES PROMOTED BY PHOSPHORUS-ACIDS

Author(s)

Aresta, M; Berloco, C; Quaranta, E

Year

1995

Is Peer Reviewed?

Journal

Tetrahedron
ISSN: 0040-4020

Publisher

PERGAMON-ELSEVIER SCIENCE LTD

Location

OXFORD

Volume

Issue

Page Numbers

8073-8088

Language

English

DOI

10.1016/0040-4020(95)00424-7

Web of Science Id

WOS:A1995RJ58400018

URL

https://linkinghub.elsevier.com/retrieve/pii/0040402095004247
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Abstract

The reaction of aromatic amines with dimethyl carbonate (DMC) or diphenyl carbonate (DPC) in the presence of organo-phosphorus acids [Ph(2)P(O)OH (1); (PhO)(2)P(O)OH (2); (BuO)(2)P(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 X(2)P(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.

Keywords

acid anhydride; aromatic amine; carbamic acid; carbamic acid ester; carbamoyl phosphate synthase; carbonic acid; phosphorus acid derivative; article; chemical reaction; priority journal; synthesis