Selective synthesis of monosubstituted and disubstituted malononitrile derivatives

CHED 441

Ryan L. Miller and Robert E. Sammelson, resammelson@bsu.edu. Department of Chemistry, Ball State University, 2000 University Ave, Muncie, IN 47306
Recently, our lab has developed a one-pot synthesis for the reductive alkylation of malononitrile to efficiently prepare monosubstituted malononitriles. Once a monosubstituted derivative has been formed, simple alkylation techniques can be used to create new derivatives. When the monosubstituted derivative contains a pyridyl or phenol substituent (from 3-hydroxybenzaldehyde, 4-hydroxybenzaldehyde, vanillin, 3-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde) alkylation is selective and disubstituted malononitriles are obtained. Reaction of the disubstituted malononitriles finally allows for pyridyl or phenol alkylation. Analogous disubstituted malononitrile derivatives have been found to be useful intermediates and/or targets for creation of numerous agricultural pesticides and pharmaceutical chemicals.