A Publication
of Reliable Methods
for the Preparation
of Organic Compounds
Annual Volume
Org. Synth. 1968, 48, 60
DOI: 10.15227/orgsyn.048.0060
[Maleonitrile, diamino-]
Submitted by J. P. Ferris and R. A. Sanchez1.
Checked by O. W. Webster and R. E. Benson.
1. Procedure
Caution! The preparation should be carried out in a hood because hydrogen cyanide may be evolved.
To a cooled (0°), stirred suspension of 10.0 g. (0.0395 mole) of aminomalononitrile p-toluenesulfonate2 in 20 ml. of water is added 10.0 g. (0.204 mole) of sodium cyanide in 30 ml. of ice water. One minute (Note 1) after the addition of the sodium cyanide the precipitated product is collected by filtration and washed with 20 ml. of ice water. The solid is immediately dissolved (Note 1) in 30 ml. of boiling isobutyl alcohol, and the solution is stirred with 0.4 g. of Darco activated carbon (Note 2) The mixture is filtered rapidly through 10 g. of Celite filter aid, and the filter cake is washed with 10 ml. of hot isobutyl alcohol. The product that crystallizes on cooling is collected by filtration and washed with 10 ml. of isobutyl alcohol to give 0.95–1.1 g. (22–26%) of white needles, m.p. 181–183° (dec.).
2. Notes
1. The product darkens on long standing.
2. Hydrogen cyanide tetramer is strongly adsorbed on activated carbon; no more than the recommended amount of carbon should be used, and it should be added carefully to avoid frothing.
3. Discussion
The present procedure is a modification of the original synthesis.3 Hydrogen cyanide tetramer can be prepared directly from hydrogen cyanide.4
4. Merits of the Preparation
This is a convenient laboratory preparation of hydrogen cyanide tetramer that avoids the hazards in using hydrogen cyanide itself. Hydrogen cyanide tetramer is a useful intermediate for the synthesis of heterocycles such as imidazoles5,6 and thiadiazoles.7
This preparation is referenced from:

References and Notes
  1. The Salk Institute for Biological Studies, San Diego, California [Present address (J.P.F.): Department of Chemistry, Rensselaer Polytechnic Institute, Troy, New York 12181].
  2. J. P. Ferris, R. A. Sanchez, and R. W. Mancuso, this volume, p. 32.
  3. J. P. Ferris and L. E. Orgel, J. Am. Chem. Soc., 88, 3829 (1966); 87, 4976 (1965).
  4. H. Bredereck, G. Schmötzer, and E. Oehler, Ann., 600, 81 (1956).
  5. H. Bredereck and G. Schmötzer, Ann., 600, 95 (1956).
  6. J. P. Ferris and L. E. Orgel, J. Am. Chem. Soc., 88, 1074 (1966).
  7. M. Carmack, L. M. Weinstock, and D. Shew, Abstracts, 136th National Meeting of the American Chemical Society, Atlantic City, N. J., Sept. 1959, p. 37P; D. Shew, Dissertation Abstr., 20, 1593 (1959).

Chemical Abstracts Nomenclature (Collective Index Number);
(Registry Number)


Hydrogen cyanide tetramer

sodium cyanide (143-33-9)

hydrogen cyanide (74-90-8)

carbon (7782-42-5)

isobutyl alcohol (78-83-1)

Maleonitrile, diamino- (1187-42-4)

Aminomalononitrile p-toluenesulfonate (5098-14-6)