Super-basic nitriles

Abstract

Alkyl substitution on the amino nitrogen, vinylogy (but not benzology), iminology, and alkyl substitution on the functional carbon of the amidine skeleton in cyanamide iminologues increase the hydrogen-bonding basicity of cyanamide and produce, on the pK_HB scale, super-basic nitriles more basic than tertiary amines. On the gas-phase basicity scale iminology also increases the basicity of cyanamide, but sp-nitrogen bases remain less basic than sp²- or sp³-nitrogen bases.