Carbon-bound diazeniumdiolates

We have been searching for compounds that contain the diazeniumdiolate functional group bound to a carbon atom which, due to the nature of the other functionality in the molecule, still spontaneously decompose to produce NO (often accompanied by nitrous oxide). We have discovered that enamines and amidines react with NO to produce such compounds as shown in structures 1 and 2, respectively. We have also shown that these reactions are applicable to small molecule mimics of polyacrylonitrile 3.

DeRosa, F., Kibbe, M.R., Najjar, S.F., Citro, M.L., Keefer, L.K. and Hrabie, J.A.  Nitric oxide-releasing fabrics and other acrylonitrile-based diazeniumdiolates.  J. Am. Chem. Soc., 129, 3786-3787, 2007.

Hrabie, J.A., Citro, M.L., Chmurny, G.N. and Keefer, L.K.  Carbon-bound diazeniumdiolates from the reaction of nitric oxide with amidines.  J. Org. Chem., 70, 7647-7653, 2005.

Arnold, E.V., Citro, M.L., Keefer, L.K. and Hrabie, J.A.  A nitric oxide-releasing polydiazeniumdiolate derived from acetonitrile.  Org. Lett., 4, 1323-1325, 2002.

Arnold, E.V., Citro, M.L., Saavedra, E.A., Davies, K.M., Keefer, L.K. and Hrabie, J.A.  Mechanistic insight into exclusive nitric oxide recovery from a carbon-bound diazeniumdiolate.  Nitric Oxide, 7, 103-108, 2002.

Hrabie, J.A., Arnold, E.V.,Citro, M.L., George, C. and Keefer, L.K.  Reaction of nitric oxide at the β-carbon of enamines.  A new method of preparing compounds containing the diazeniumdiolate functional group.  J. Org. Chem., 65, 5745-5751, 2000.

Arnold, E.V., Keefer, L.K. and Hrabie, J.A.  Reaction of nitric oxide with benzyl cyanide to yield a bis-diazeniumdiolated imidate.  Tetrahedron Lett., 41, 8421-8424, 2000.