Aminolysis Reaction of Glycerol Carbonate in Organic and Hydroorganic Medium

Abstract

Aminolysis reaction of glycerol carbonate with primary amine in organic and hydroorganic media leads to the formation of two hydroxyurethane isomers and a partial decomposition of glycerol carbonate into glycerol. Aminolysis with a secondary amine promotes the condensation reaction and limits the formation of glycerol. The ratio of a versus b was determined by zgig 13 C NMR. This technique permits computing the yield of a and b products in the medium. The quantity of glycerol was determined by GC analysis. The ratio of the isomers and the amount of glycerol depend on the amine and the solvent. Kinetic investigations reveal that, in hydroorganic medium, the more the alkyl chain of the amine increased, the less glycerol was formed. On the contrary, in organic medium, the alkyl chain of the amine does not play a major role in the formation of glycerol.

Utilization of cyclocarbonated lignin as a bio-based cross-linker for the preparation of poly(hydroxy urethane)s

“…It is worth noticing that the intensity of both these peaks is higher if compared to the reference prole of acetylated cyclocarbonated lignin (grey line) and, particularly, that the population of the signal pertaining to the carbonyls of acetylated secondary hydroxyls are larger. Therefore, new alcoholic functionalities are formed aer the addition of DAD to cyclic carbonates and, in agreement with several publications, [28][29][30] the formation of secondary hydroxyl groups was predominantly observed. Moreover, at 169.2 ppm is found a sharp peak related to carbonyl carbon atoms arising from N-acetylation (atoms number 18 in Scheme 1).…”

From the Synthesis of Biobased Cyclic Carbonate to Polyhydroxyurethanes: A Promising Route towards Renewable Non‐Isocyanate Polyurethanes

“…The amine can also attack the urethane group formed after aminolysis by transurethanization, leading to urea formation . Furthermore, the surprising presence of glycerol as a byproduct of the aminolysis reaction was recently highlighted, after the decomposition of GC through a hydrolysis process. The glycerol yield largely depends on both the amine reactivity and water content in the media.…”

“…The amine can also attack the urethane group formed after aminolysis by transurethanization, leadingt ou rea formation. [67] Furthermore, the surprising presence of glycerol as ab yproduct of the aminolysis reaction was recently highlighted, [68] after the decom-Scheme7.Possibler eactions between a5CC anda mine:1)conventional aminolysis,2 )carbonation of the amine, (3) in situ CO 2 formation,4 )urea formation by transurethanization, 5) amidification reaction,a nd (6) oxazolidinone formation by dehydration. [4] positiono fG Ct hrough ah ydrolysis process.…”

Fatty Ester-Based Hydroxy Carbamates - Synthesis and Investigation as Lubricant Additives

“…Whereas primary aliphatic amines were reacted at room temperature and mostly at only a slight surplus of the amine in order to minimize amide formation, the secondary amines were converted at a higher temperature of 120 °C. This requirement has already been shown by kinetic studies of Bürgel et al and Nohra et al The latter reactions were carried out in autoclaves. The pressure of inert gas was applied to hold the amines completely in the liquid phase.…”