Diaminomaleonitrile was first isolated in 1873 as a black solid, when it was recognized as a polymer of hydrogen cyanide with the formula (HCN)x.[3] It was identified as the tetramer (HCN)4 by
ebullioscopy in 1923.[4] The cis-configuration of the amino groups was shown in 1928 through reaction with
glyoxal to give 2,3-diaminopyrazine, and the full structure was shown in 1955 to be diaminomaleonitrile, as opposed to the
isomeric aminoiminosuccinonitrile (AISN).[5]
It can be prepared by cyanation of aminomalonitrile.[6][7]
Possible role in abiogenesis
Diaminomaleonitrile has been proposed since the 1960s as a key substance for the prebiotic synthesis of
nucleobases. Photochemical rearrangement of DAMN under UV light gives 4-aminoimidazole-5-carbonitrile (AICN), which can react further to form various nucleobases.[8][9]
Early experiments have also suggested that certain amino acids, such as
aspartic acid,
alanine, and
glycine, may have their probiotic origins in the acidic hydrolysis of diaminomaleonitrile.[10][11]
Due to the ubiquity of hydrogen cyanide and its oligomers in space, it has been proposed that the dark material found in comets may consist of diaminomaleonitrile and higher oligomers, and that such polymers of HCN may have covered the surface of the early Earth.[12][13]
^Al-Azmi, A.; Elassar, A.-Z. A.; Booth, B. L. (2003). "The Chemistry of Diaminomaleonitrile and its Utility in Heterocyclic Synthesis". Tetrahedron. 59 (16): 2749–2763.
doi:
10.1016/S0040-4020(03)00153-4.