Bonding in Functionalized Aziridines: Nitrogen-15 and Carbon-13 Studies

Two isomeric pairs of cis- and trans-1-cyclohexyl-2-phenyl-3-benzoylaziridines have been synthesized: (1) with a nitrogen-15 labelled nitrogen, and (2) with carbon-13 labelled ring carbons. The carbon-13 to X (where X=nitrogen-15, carbon-13 or hydrogen-I) spin-spin coupling constants were measured and interpreted in terms of stereoelectronic effects. X-ray crystallographic data (earlier determined for cisand trans-1-cyclohexyl-2-phenyl-3-(p-toluyl)aziridines)1 appear in good agreement with the NMR data. Bonding is discussed for the three-ring itself (NMR studies) and for its substituents (X-ray studies). It is concluded that stereochemical interaction of the Van der Waals type is an important determinant of aziridine bond length. Three-ring to carbonyl hyperconjugation is correlated with stereoelectronic interactions in the trans isomer

Bonding in Functionalized Aziridines: Nitrogen-15 and Carbon-13 Studies

Two isomeric pairs of cis- and trans-1-cyclohexyl-2-phenyl-3-benzoylaziridines have been synthesized: (1) with a nitrogen-15 labelled nitrogen, and (2) with carbon-13 labelled ring carbons. The carbon-13 to X (where X=nitrogen-15, carbon-13 or hydrogen-I) spin-spin coupling constants were measured and interpreted in terms of stereoelectronic effects. X-ray crystallographic data (earlier determined for cisand trans-1-cyclohexyl-2-phenyl-3-(p-toluyl)aziridines)1 appear in good agreement with the NMR data. Bonding is discussed for the three-ring itself (NMR studies) and for its substituents (X-ray studies). It is concluded that stereochemical interaction of the Van der Waals type is an important determinant of aziridine bond length. Three-ring to carbonyl hyperconjugation is correlated with stereoelectronic interactions in the trans isomer