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--
- Journal Information:
- American Chemical Society, Division of Petroleum Chemistry, Preprints; (USA), Journal Name: American Chemical Society, Division of Petroleum Chemistry, Preprints; (USA) Vol. 32:1; ISSN 0569-3799; ISSN ACPCA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Acetylene-mediated alkylation of monoalkyl carbonates and carbamic acids with tert-amines
Catalytic reaction of pi-allyl complexes of palladium with allyl O and N nucleophiles, a new promising route for synthesis of C/sub 16/ amines and ethers
Related Subjects
020500* -- Petroleum-- Products & By-Products
AMINES
CARBAMATES
CARBONIC ACID DERIVATIVES
CARBONYLATION
CARBOXYLIC ACID SALTS
CATALYSIS
CATALYSTS
CATALYTIC EFFECTS
CHEMICAL PREPARATION
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
DATA
ELEMENTS
EXPERIMENTAL DATA
INFORMATION
KINETICS
MEDIUM PRESSURE
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDATION
OXYGEN
PALLADIUM COMPOUNDS
REACTION KINETICS
SYNTHESIS
TRANSITION ELEMENT COMPOUNDS
YIELDS