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Incorporation and deoxygenation of carbon dioxide: A metal‐assisted facile conversion of carbon dioxide and primary amines to isocyanates
Author(s) -
Belforte Antonio,
Dell'Amico Daniela Belli,
Calderazzo Fausto
Publication year - 1988
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19881211104
Subject(s) - chemistry , isocyanate , medicinal chemistry , polymer chemistry , decarboxylation , amine gas treating , metal , primary (astronomy) , organic chemistry , catalysis , physics , astronomy , polyurethane
Metal N ‐alkylcarbamato complexes [M(O 2 CNHR) n ] (M = Na, n = 1; M = Mn, Co, n = 2) were prepared by treating CO 2 with a primary amine RNH 2 (R = Ph, Cy, Pr) and various complex precursors. For M = Mn or Co and R = Cy, MCl 2 can be used as starting material. These complexes were readily decomposed by acyl halides R′COCl (R′ = Ph, Me), and two reaction pathways were observed. One led to decarboxylation and formation of amides RNHC(O)R′, while the other afforded isocyanate RNCO and carboxylic acid (M = Na) or carboxylic anhydride (M = Mn, Co). Analysis of the reaction products showed that the metal plays a major rǒle in the formation of the isocyanate, intercepting one of the reaction products. A mechanistic rationalization is proposed.