Fourier transform infrared spectroscopy studies of cyanide ion solutions of dimethylformamide and aqueous dimethylformamide

Fourier transform infrared spectroscopy has been used to investigate the behaviour of HCN and alkali metal and tetraethylammonium cyanides in DMF and aqueous DMF. The cyanide ion exists as free ions and ion pairs in pure DMF but as water-solvated and DMF-solvated ions in aqueous DMF. The aqueous DMF solutions can be treated as a pseudo two-phase system with a distribution coefficient of 0.018 between the aqueous and DMF-rich pseudo phases. A kinetic analysis of the cyanide ion – benzyl chloride reaction in DMF and aqueous DMF has shown that the rate constant for the SN2 reaction is markedly decreased with the addition of as little as 2.5% water. This decrease is primarily due to changes in transition state solvation. The SN2 reactions between cyanide ion and benzylmethyl-4-substituted phenylsulphonium perchlorates in 20% aqueous DMF have also been investigated.