Eco‐Efficient Synthesis of Cyclic Carbamates/Dithiocarbonimidates from Cyclic Carbonates/Trithiocarbonate and Aromatic Amines Catalyzed by Ionic Liquid BmimOAc

Abstract

We have investigated the reactions of cyclic carbonates/trithiocarbonate and aromatic amines in the presence of a basic ionic liquid, 1butyl-3-methylimidazolium acetate (BmimOAc), which produced various cyclic carbamates/dithiocarbonimidates in fairly good to excellent yields. The use of BmimOAc as catalyst here not only offers an effective approach to the synthesis of the target compounds, but also avoids the use of conventional toxic materials. By means of the reactions of cyclic carbonates and aromatic amines, 3-aryloxazolidin-2-ones, 3,3'-aryldioxazolidin-2-ones and 3-arylA C H T U N G T R E N N U N G [1,3]oxazinan-2-ones could be synthesized. NMR spectroscopy and DFT calculations revealed that both the cation and the anion of BmimOAc activate cooperatively the substrates in these reactions by means of inducing hydrogen bonding. In addition, condensation reactions of ethylene trithiocarbonate and aromatic amines also proceeded very well in the presence of the BmimOAc catalyst, which opened a hitherto unreported route to [1,3]dithiolan-2-ylidene-arylamine derivatives in a straightforward way.

DBU and DBU‐Derived Ionic Liquid Synergistic Catalysts for the Conversion of Carbon Dioxide/Carbon Disulfide to 3‐Aryl‐2‐oxazolidinones/[1,3]Dithiolan‐2‐ylidenephenyl‐ amine

“…However, it suffers from a tedious and wasteful multistep operational procedure. Recently, the preparation of [1,3]dithiolan‐2‐ylidene aryl amines by the reaction of ethylene trithiocarbonate and aromatic amines has also been developed . To the best of our knowledge, this is the first report on the direct preparation of 2 a from CS 2 , EO, and aniline in a one‐pot reaction (Table ).…”

A theoretical study of the substituent effect on reactions of amines, carbon dioxide and ethylene oxide catalyzed by binary ionic liquids

“…4,11,12 The synergistic catalysis in which a few catalysts are combined together is one of efficient strategies to convert CO 2 . [13][14][15][16][17] In this strategy, one way is to use various ionic liquids to catalyze CO 2 conversion to oxazolidinone [18][19][20] whose derivatives are widely used in the pharmaceutical eld due to their remarkable bioactivity. [21][22][23][24] Recently, Wang et al 18 reported the one-pot conversion of CO 2 , ethylene oxide (EO) and amines to 3-aryl-2-oxazolidinones, which are catalyzed by the binary ionic liquids, 1-butyl-3-methyl-imidazolium bromide (BmimBr) and 1-butyl-3-methyl-imidazolium acetate (BmimOAc).…”

Sustainable conversion of carbon dioxide: the advent of organocatalysis

“…Gao's group recently reported 122,123 an alternative strategy for the selective preparation of 3-substituted cyclic carbamates from the reaction between a cyclic carbonate (made using CO 2 ) and aromatic amines using 1-butyl-3-methylimidazolium acetate (BmimOAc) as catalyst (Scheme 14). DFT calculations revealed that both the cationic and the anionic moieties of the catalyst activate in a cooperative fashion the substrates (i.e., cyclic carbonates and aromatic amines) by means of hydrogen-bonding.…”