Electrochemically Promoted C−N Bond Formation from Amines and CO₂ in Ionic Liquid BMIm−BF₄:  Synthesis of Carbamates

Abstract

A new electrochemical procedure for the synthesis of organic carbamates from amines and carbon dioxide has been developed using selective cathodic reduction of carbon dioxide in CO2-saturated room-temperature ionic liquid BMIm-BF4 solutions containing amines 1a-j, followed by addition of EtI as an alkylating agent. The synthesis was carried out under mild (PCO2 = 1.0 atm, t = 55 degrees C) and safe conditions, and the use of volatile and toxic solvents and catalysts (according to the growing demand for ecofriendly synthetic methodologies), as well as of any supporting electrolyte (for a very easy workup of the reaction mixture), was avoided. Carbamates 2a-j were isolated in good to high yields.

A novel electrochemical conversion of CO 2 with aryl hydrazines and paraformaldehyde into 1,3,4-oxadiazol-2(3 H )-one derivatives in one step

“…Feroci and co-workers achieved electrochemical synthesis of carbamates from CO 2 and amines in ionic liquid BMIm-BF 4 [7]. In the past decade, great progress has been made in the utilization of CO 2 [8,9].…”

Electrocarboxylation of Carbon Dioxide with Polycyclic Aromatic Hydrocarbons Using Ni as the Cathode

“…So for, many researches have been made in this area. For example, with metal Al or Mg as a sacrificial anode, the electrochemical reaction of CO 2 with some organic compounds, including organic halides, [1][2][3][4][5][6][7][8] ketones, [9][10][11][12] alkenes, 13,14 alkynes, [15][16][17] epoxides, 18,19 amines, 20 and heterocyclic compounds, [21][22][23] could afford valuable compounds under mild conditions.…”

Electrocarboxylation of Alkynes with Carbon Dioxide in the Presence of Metal Salt Catalysts

“…[3][4][5] In the last 50 years, many research groups have been devoted to study the fixation and conversion of CO 2 with various substrates involving alkenes, [6][7][8][9][10] alkynes, 5,[11][12][13] ketones, [14][15][16] halides, [17][18][19][20][21][22][23] epoxides [24][25] and imines. 26 The electrochemical fixation of CO 2 into the unsaturated hydrocarbons to form new carbon-carbon bonds is an interesting topic because it could afford valuable fine chemicals. By now, the electrocarboxylation of nonactivated and unsaturated hydrocarbons with CO 2 have been reported in the presence of catalysts 5,12 or only depending on the nature of the cathode material used.…”