Oxamates as 1,2‐Diketone Equivalents: The Effect of Fluorine

Abstract

AbstractOxamates as building blocks play an important role in organic and bioorganic chemistry as well as in coordination chemistry and material sciences. In this paper, we present new fluorinated derivatives, which are synthesized from selected fluorinated primary amines RFNH2 (RF=CH2CF3, CH2CHF2, CH2CF2CH3, CH(CF3)2, CH(CH3)CF3) or their hydrochlorides and ethyl oxalylchloride. Since oxamates can be considered as 1,2 diketones, we investigated their properties, geometries, effective charges at oxygen and nitrogen and the pKa values for the N−H grouping. In two cases, the molecular structures have been measured by XRD, observing almost planar arrangement of C2−N1−C3−C4 atoms. The effect of fluorine is discussed and compared with non‐fluorinated oxamates. The effective charges can be controlled by various alkyl substituents at nitrogen (branched or straight, fluorinated or non‐fluorinated) and could open a new field, especially when fluorinated, for multiple applications in material sciences (surfaces) and biochemical systems (enzymes).