Cyanomethyl anion/carbon dioxide system: an electrogenerated carboxylating reagent. Synthesis of carbamates under mild and safe conditions.
A new carboxylating reagent ((-)CH(2)CN/CO(2)) was obtained by bubbling CO(2) in a CH(3)CN-TEAP (tetraethylammonium perchlorate) solution previously electrolyzed under galvanostatic control. Organic carbamates were isolated from these solutions after addition of amines and an alkylating agent. In this paper, we describe the optimized conditions for the electrochemical synthesis of carbamates from amines and CO(2), in mild and safe conditions, without any addition of bases, probases, or catalysts. Carbamates were isolated from primary and secondary aliphatic amines in high to excellent yields and from aromatic amines in moderate yields (dependent on the nucleophilicity of the nitrogen atom).
Feroci
Marta
M
Dip. Ingegneria Chimica, Materiali, Materie Prime e Metallurgia, Università La Sapienza, via Castro Laurenziano, 7, I-00161 Roma, Italy. marta.feroci@uniroma1.it
Casadei
Maria Antonietta
MA
Orsini
Monica
M
Palombi
Laura
L
Inesi
Achille
A