The present study describes the clean synthesis of non-phosgene organic carbonates (NPOCs) from a selective multicomponent reaction with two important by-products from sugar and alcohol industries, namely, fusel alcohols and carbon dioxide, in the presence of 1,8-diazabicycloundecene (DBU), 1,5-diazabicyclo[4.3.0]-non-5-ene (DBN) or 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]-pyrimidine (TBD) and an alkylating agent. The bases were used for the nucleophilic activation of the alcohols. The synthesis of carbonates was carried out without solvent and confirmed by GC-MS with EI ionization mode, 1 H-and 13 C-NMR and FT-IR analysis. The carbonates were obtained in excellent yields. Crude fusel alcohol can be converted to alkylcarbonates. The proposed methodology can also be employed to convert other hydroxylated compounds into carbonates.

Dimethyl sulfoxide ruthenium(II) complexes of N-heterocyclic carbenes derived from cycloalkylamines (cycloalkyl = cyclopentyl (1a), cyclohexyl (1b), cycloheptyl (1c), and cyclooctyl (1d)) were synthesized: [RuCl 2 (Sdmso) 2 (IPent)] (2a), [RuCl 2 (S-dmso) 2 (IHex)] (2b), [RuCl 2 (S-dmso) 2 (IHept)] (2c), and [RuCl 2 (S-dmso) 2 (IOct)] (2d). The imidazolium salts 1a-1d were characterized by FTIR, UV-vis, and 1 H and 13 C NMR spectroscopy, while their respective dimethyl sulfoxide ruthenium(II) complexes (2a-2d) were characterized by elemental analysis, FTIR, UV-vis, 1 H and 13 C NMR, and cyclic voltammetry. The complexes 2a-2d were evaluated as catalytic precursors for ROMP of norbornene (NBE) and for ATRP of methyl methacrylate (MMA). The polynorbornene (polyNBE) syntheses via ROMP using the complexes 2a-2d as pre-catalysts were evaluated under reaction conditions of [EDA]/[Ru] = 28 (5 μL), [NBE]/[Ru] = 5000 at 50°C as a function of time. The polymerization of MMA via ATRP was conducted using the complexes 2a-2d in the presence of ethyl 2-bromoisobutyrate (EBiB) as the initiator. All tests were using the molar ratio [MMA]/[EBiB]/[Ru] = 1000/2/1 and conducted at 85°C. The linear correlation of ln([MMA] 0 /[MMA]) and time clearly indicates that the concentration of radicals remains constant during the polymerization and that the ATRP of MMA mediated by 2a-2d proceeds in a controlled manner.