1.1- Enediamines nitration

Abbreviations Amm Ammonium DNB Dinitrobenzene DNN Dinitronaphthalene DNDFhA Dinitrodiphenylamine GuN Guanidine nitrate HNDPhA Hexanitrodiphenylamine PETN Pentaerythritol Tetranitrate PH- olx Ethyl-enediamine Dinitrate RDX Cyclonite, or Hexogen TNT Trinitrotoluene TNX Trinitroxylene. 

Recently, Baum and coworkers154 reported the nitration of 1,1-diamino-2,2-dini-troethylene. On treatment with nitric acid and trifluoroacetic anhydride in methylene chloride at 0 °C, 1,1-enediamines 42 are converted to 3-nitro-2-(trinitromethyl)-l,3-diazacyclic compounds 192 in good yields (equation 79). Compounds 192 have also been prepared from the nitration of 7, although the yields are lower (16-22%). Denitration of 192 to 193 includes a reductive denitration of 192 with potassium iodide and acidification of initially formed salts of 193. Nitration of 193 regenerates 192 (equation 79). 

Several preparations of salts of the czs-dinitrobis(ethyl-enediamine)cobalt(III) ion have been reported in the literature. The most usual is that of Werner/ modified by Holtzclaw, Sheetz, and McCarty, beginning with potassium hexanitrocobaltate(III). However, this method makes use of a starting material which is difficult to prepare in high purity and to dry thoroughly, involves critical temperature control, and produces a yield of about 15%. The following procedure, which utilizes ethylenedi-amine)cobalt(III) chloride as the starting material, provides a 60% yield of cfs-dinitrobis(ethylenediamine)cobalt-(III) nitrite. The nitrite is then easily converted to the nitrate. 

The as-bromoamminebis(ethylenediamine)cobalt(III) bromide crystallizes in purple platelets. The compound has been resolved/ and the kinetics of the reactions of hydroxide ion with the d- and Z-isomers in water have been determined. The red-orange crystals of as-aquoammine-bis(ethylenediamine)cobalt(III) bromide are compact and almost cubic, in contrast to the orange needle-plates of the trans isomer. The crystals of water exchange of the aquoammine complexes have been studied. ... 

Dinitro-bis(et1iy[enediamine)cobalt (III) nitrates, cis- and rrans- forms. Prepn and properties ace given in Ref 2. 

Procedure (b) The residue was nitrated as in procedure (a) and dissolved in 50% ethanol (10 ml). The ethanolic solution was heated on a water bath with 10% HC1 (2.5 ml) and zinc dust (0.1 g) for 10 minutes, cooled and filtered. The zinc residue was washed with water and the washings were added to the filtrate. 1% NaN02 (1 ml) was added, mixed and allowed to stand for 10 minutes. 2.5% solution of ammonium sulfamate (1 ml) was added, the mixture was shaked and allowed to stand for 10 minutes. 2.5% solution of ammonium sulfamate (1 ml) was added, the mixture was shaked and allowed to stand for 10 minutes. 1% N-l-naphthylethyl-enediamine dihydrochloride solution (1 ml) was added and diluted to 25 ml with water. The extinction of the produced color was measured after 30 minutes at 550 nm. The concentration was calculated by reference to a standard curve. Recovery experiments in both procedures indicated an accuracy of 1%. 

Another example of dissolving metals in ILs is linking a complex to an IL. Tan et al. synthesized a series of salen Mn(III) complexes functionalized by l-propylamine-3-methylimidazolium tetrafluoroborate ILs [180], Iida et al. have reported an interesting set of Ag-based ILs, bis(/V-2-c(hylhcxylethylenediamine) silver nitrate, [Ag(eth-hex-en)2]N03, and bis(/V-hex yI et hyI enediamine)silvertl) hexafluorophosphate, [Ag(hex-en)2]PF6 [181], which are precursors for silver nanoparticles (Fig. 8). 

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