[1187-42-4]  · C4H4N4  · Diaminomaleonitrile  · (MW 108.10)

(useful for a preparation of substituted imidazoles,2,4-6 pyrazines,9-13 and nucleosides14)

Alternate Name: DAMN.

Physical Data: mp 184 °C (dec); sublimes at 120 °C/0.1 mmHg; dipole moment 7.9 D; pKb 2.18; heat of combustion 5230 cal g-1; d 1.29 g cm-3.

Solubility: 25 °C (g/100 mL): acetone (15), DMA (39), water (0.5), THF (14), MeCN (7), EtOAc (3.6), ether (0.4), MeOH (6.1), EtOH (3.6), isopropanol (2.6), dioxane (9.6).

Preparative Methods: can be prepared from HCN by oligomerization1d or by hydrogenation of diiminosuccinonitrile.1a

Handling, Storage, and Precautions: the title reagent has an ALD of 450 mg/kg in rats; use in a fume hood.

Heterocycle Synthesis.

Diaminomaleonitrile is a weakly basic diamine with similar reactivity to o-phenylenediamine. DAMN has been used to prepare a variety of heterocyclic compounds. 4,5-Dicyanoimidazole was synthesized by refluxing DAMN and Triethyl Orthoformate in anisole (eq 1).2 One possible intermediate can also be isolated under different reaction conditions (eq 2).3 Cyanogen chloride or N-dichloromethylenephenylsulfonamide reacts with DAMN to give aminodicyanoimidazole or 4,5-dicyano-2-phenylsulfonylaminoimidazole, respectively (eqs 3 and 4).4,5

5-Amino-4-(C-cyanoformimidoyl)-1,2-dimethylimidazole was made by controlled basification of the salt which was formed from DAMN and nitrilium triflate (eq 5).6

An efficient synthesis of 3,4-dicyano-1,2,5-thiadiazole was accomplished by reaction of DAMN with Thionyl Chloride (eq 6).7

Phosphorus(III) Chloride reacts with DAMN to yield 2-chloro-2,3-dihydro-1H-1,3,2-diazaphosphole-4,5-dinitrile (eq 7).8

Substituted pyrazines can be prepared by condensation of DAMN with either 1,2-diketones or b-keto sulfoxides or acylsulfonium halides (eqs 8-10).9-11

Oxalyl Chloride or ethyl ethoxycarbonylformimidate reacts with DAMN to afford pyrazine derivatives (eqs 11 and 12).12,13

DAMN has been proposed to be an essential intermediate to purines in prebiotic origins of life and it has been used to prepare some nucleosides (eq 13).14

1. (a) Webster, O. W.; Hartter, D. R.; Begland, R. W.; Sheppard, W. A.; Cairncross, A. JOC 1972, 37, 4133. (b) Begland, R. W.; Hartter, D. R.; Jones, F. N.; Sam, D. J.; Sheppard, W. A.; Webster, O. W.; Weigert, F. J. JOC 1974, 39, 2341. (c) Ohtsuka, Y. JOC 1976, 41, 629. (d) Bredereck, H.; Schmoetzer, G.; Oehler, E. LA 1956, 81, 600.
2. O'Connell, J. F.; Parquette, J.; Yelle, W. E.; Wang, W.; Rapoport, H. S 1988, 767.
3. Alves, M. J.; Booth, B. L.; Fernanda, M.; Proenc, J. R. P. JCS(P1) 1990, 1705.
4. Sheppard, W. A.; Webster, O. W. JACS 1973, 95, 2697.
5. Merchán, F. L.; Garín, J.; Tejero, T. S 1982, 984.
6. Booth, B. L.; Coster, R. D.; Fernanda, M.; Proenca, J. R. P. JCS(P1) 1987, 1521.
7. Warren, J. D.; Lee, V. J.; Angier, R. B. JHC 1979, 16, 1617.
8. Karaghiosoff, K.; Sheldrick, W. S.; Schmidpeter, A. CB 1986, 119, 3213.
9. Popp, F. D. JHC 1974, 11, 79.
10. Kano, S.; Yuasa, Y. H 1981, 16, 1449.
11. Kano, S.; Takahagi, Y.; Shibuya, S. S 1978, 372.
12. Suzuki, T.; Nagae, Y.; Mitsuhashi, K. JHC 1986, 23, 1419.
13. McKillop, A.; Henderson, A.; Ray, P. S.; Avendano, C.; Molinero, E. G. TL 1982, 23, 3357.
14. Ferris, J. P.; Devadas, B.; Huang, C.-H.; Ren, W.-Y. JOC 1985, 50, 747.

Seung Hoon Cheon

Sandoz Research Institute, East Hanover, NJ, USA

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