Download PDF
Synlett 2013; 24(4): 519-521
DOI: 10.1055/s-0032-1318142
letter
© Georg Thieme Verlag Stuttgart · New York

Nucleophilic Reactions of The Bis Ammonium Salt of 4,4′,5,5′-Tetranitro-2,2′-biimidazole

Megan M. Breiner
a   Los Alamos National Laboratory, Weapons Experiments Division, Los Alamos, NM 87545, USA   Fax: +1(505)6670500   Email: dechavez@lanl.gov
,
David E. Chavez*
a   Los Alamos National Laboratory, Weapons Experiments Division, Los Alamos, NM 87545, USA   Fax: +1(505)6670500   Email: dechavez@lanl.gov
,
Damon A. Parrish
b   Naval Research Laboratory, Laboratory for the Structure of Matter, Washington, DC 20375, USA
› Author Affiliations
Further Information

Publication History

Received: 10 December 2012

Accepted after revision: 10 January 2013

Publication Date:
29 January 2013 (online)

    Permissions and Reprints All articles of this category


Abstract

The reactivity of the bis ammonium salt of 4,4′,5,5′-tetranitro-1,1′-biimidazole toward nucleophilic addition to the electrophiles dimethylsulfate and mesitylene-O-sulfonyl hydroxylamine has been studied. We have found that the tetranitrobiimidazolate bis anion has sufficient nucleophilicity to react with these electrophiles to form new products, 1,1′-dimethyl-4,4′,5,5′-tetranitro-2,2′-biimidazole (DMTNBI), 1,1′-diamino-4,4′,5,5′-tetranitro-2,2′-biimidazole, and ammonium 1-amino-4,4′,5,5′-tetranitro-2,2′-biimidazolate. These materials were characterized chemically and with respect to their thermal stability.

Key words

biimidazoles - heterocycles - N-amination - explosives - nitro compounds

Supporting Information

  • Supporting Information
    • for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
 

  • References

  • 1 De Carneri I. NATO Adv. Study Inst. Ser., Series A: Life Sciences 1982; 42: 115
  • 2 Mukherjee T, Boshoff H. Future Med. Chem. 2011; 3: 1427
    Crossref
  • 3 Lui K, Zhu H.-L. Anti-Cancer Agents Med. Chem. 2011; 11: 687
    Crossref
  • 4 Al-Masoudi NA, Pfleiderer W, Pannecouque C. Z. Naturforsch., B 2012; 67: 835
    • 5a Damavarapu R, Neno RS, Duddu R, Zhang M.-X, Dave PR International Annual Conference of ICT, 37th (Energetic Materials) 2006, Karlsruhe, Germany, 17/1–17/5.
    • 5b Coburn MD. US Patent US4028254, 1977
    • 5c Liu H-J, Cao D.-L, Li Y.-X, Wang J.-L. Hanneng Cailiao 2005; 13: 269
  • 6 Damavarapu R, Jayasuriya K, Vladimiroff T, Iyer S. US Patent US5387297, 1995
    • 7a Ravi P, Badgujar DM, Gore GM, Tewari SP, Sikder AK. Prop. Explos. Pyrotech. 2011; 36: 393
      Crossref
    • 7b Cho JR, Kim KJ, Cho SG, Kim JK. J. Heterocycl. Chem. 2002; 39: 141
      Crossref
    • 7c Wang W, Yang W, Ji Yueping Ding F. Huozhayao, Xuebao 2008; 31: 32
    • 7d Duddu R, Zhang M-X, Damavarapu R, Gelber N. Synthesis 2011; 2859
      Article in Thieme Connect
    • 7e Wang J., Huang J.-l., Zhang X.-y., Zhou X.-q., Li J.-s.; International Annual Conference of ICT, 43rd (Energetic Materials) 2012, Karlsruhe, Germany, 75/1–75/5.
    • 8a Melloni P, Dradi E, Logemann W, De Carneri I, Trane F. J. Med. Chem. 1972; 15: 926
      Crossref
    • 8b Melloni P, Metelli R, Fusar Bassini D, Confalonieri C, Logemann W, De Carneri I. Arzneim.-Forsch. 1975; 25: 9
    • 8c Barnett M, Secondo P, Collier H. J. Heterocycl. Chem. 1996; 33: 1363
      Crossref
    • 8d Semenov VV, Ugrak BI, Shevelev SA, Kanishchev MI, Baryshnikov AT, Fainzil’berg AA. Izv. Akad. Nauk, Ser. Khim. 1990; 8: 1827
  • 9 Klapoetke TM, Preimesser A, Stierstorfer J. Z. Anorg. Allg. Chem. 2012; 1278
    • 10a Kim JK, Kim SE, Kim HS. US Patent Appl., US20120203008, 2012
    • 10b Cho SG, Cho JR, Goh EM, Kim J.-K, Damavarapu R, Surapaneni R. Prop. Explos. Pyrotech. 2005; 30: 445
      Crossref
    • 10c Chavez DE, Parrish D, Preston DN, Mares IW. Prop. Explos. Pyrotech. 2012; 37: 647
      Crossref
  • 11 Cromer DT, Storm CB. Acta Crystallogr., Sec. C 1990; C46: 1959
    Crossref
  • 12 Mendiola J, Rincon JA, Mateos C, Soriano JF, de Frutos O, Niemeier JK, Davis EM. Org. Process Res. Dev. 2009; 13: 263
    Crossref
  • 13 Synthesis of Compounds 4 and 5: Mesitylene O-sulfonyl hydroxylamine (MSH; 0.43 g, 2 mmol) was added to a solution of bisammonium 4,4′,5,5′-tetranitro-2,2′-bi-1H-imidazolate, (0.348 g, 5.75 mmol) in DMF (5 mL) and stirred at 25 °C for 18 h without stirring. The reaction mixture was poured into H2O (20 mL). The mixture was extracted with CHCl3 (2 × 10 mL). The organics were dried with MgSO4, and concentrated. The residue was purified by column chromatography (EtOAc) to provide compound 5; yield: 0.137 g (40%); mp 206 °C (dec.). IR (KBr): 3362, 3260, 1559, 1533, 1502, 1389, 1362, 1327, 1145, 1046, 851, 816, 760, 748, 708, 641 cm–1. 1H NMR (300 MHz, CD3CN): δ = 7.1. 13C NMR (100 MHz, DMSO-d 6): δ = 136.07, 138.70, 141.85. Anal. Calcd for C6H4O8N10: C, 20.94; H, 1.17; N, 40.70. Found: C, 20.92; H, 1.16; N, 40.71. The aqueous solution was allowed to stand for 3 d and compound 4 was crystallized from solution; yield: 0.104 g (30%); mp 233 °C (dec.). IR (KBr): δ = 3337, 3297, 2935, 2816, 1536, 1513, 1464, 1437, 1402, 1365, 1313, 1265, 1174, 1111, 1001, 935, 855, 818, 809, 772, 764, 722, 694 cm–1. 1H NMR (300 MHz, DMF-d 7): δ = 7.2 (br s, 2 H), 7.69 (t, J = 12.9 Hz, 4 H). 13C NMR (100 MHz, DMSO-d 6): δ = 132.30, 135.85, 136.63, 137.98, 139.48, 141.10. Anal. Calcd for C6H4O8N10: C, 20.82; H, 1.75; N, 40.46. Found: C, 20.90; H, 1.77; N, 40.47.
  • 14 CCDC 908704 and CCDC 908705 contain the supplementary crystallographic data for 2 and 4. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.