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Title: Oxidative carbonylation of amines to carbamates

Within the last several years, new technologies have appeared to replace phosgene for isocyanate manufacture. These include carbamate chemistries based upon dialkyl carbonate, reductive carbonylation of nitroaromatics, and oxidative carbonylation of amines. The carbamate ester can be handled safely and is reversibly cleaved to the isocyanate. The technology described here involves the preparation of both aliphatic and aromatic carbamates from an amine, alcohol, CO, oxidant, and a non-corrosive catalyst. The catalyst precursor is Pd(OAc){sub 2} and the oxidants are copper carboxylates or copper carboxylates and molecular oxygen. The latter represents a one-step carbamate synthesis with high catalyst activity, nearly quantitative conversions and alcohol selectivities greater than 90%. Operating temperatures and pressures are 80-110{degree}C and less than 500 psi, respectively. Experiments designed to probe the mechanism will be presented along with a discussion of novel (Cu(O{sub 2}CR){sub 2}){sub 2}R'NH{sub 2} complexes.
Authors:
Publication Date:
OSTI Identifier:
5276772
Report Number(s):
CONF-8704363--
Journal ID: ISSN 0569-3799; CODEN: ACPCA
Resource Type:
Conference
Resource Relation:
Journal Name: American Chemical Society, Division of Petroleum Chemistry, Preprints; (USA); Journal Volume: 32:1; Conference: American Chemical Society Division of Petroleum Chemistry, Denver, CO (USA), 5-10 Apr 1987
Country of Publication:
United States
Language:
English
Subject:
02 PETROLEUM; AMINES; CARBONYLATION; OXIDATION; CARBAMATES; CHEMICAL PREPARATION; PALLADIUM COMPOUNDS; CATALYTIC EFFECTS; CATALYSIS; CATALYSTS; CHEMICAL REACTION KINETICS; CHEMICAL REACTION YIELD; EXPERIMENTAL DATA; MEDIUM PRESSURE; MEDIUM TEMPERATURE; OXYGEN; CARBONIC ACID DERIVATIVES; CARBOXYLIC ACID SALTS; CHEMICAL REACTIONS; DATA; ELEMENTS; INFORMATION; KINETICS; NONMETALS; NUMERICAL DATA; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; REACTION KINETICS; SYNTHESIS; TRANSITION ELEMENT COMPOUNDS; YIELDS 020500* -- Petroleum-- Products & By-Products