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.
- OSTI ID:
- 5276772
- Report Number(s):
- CONF-8704363-; CODEN: ACPCA
- Journal Information:
- American Chemical Society, Division of Petroleum Chemistry, Preprints; (USA), Vol. 32:1; Conference: American Chemical Society Division of Petroleum Chemistry, Denver, CO (USA), 5-10 Apr 1987; ISSN 0569-3799
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
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