Synthesis of ?-functional nitro compounds by the nitration of activated carbonyl compounds in a two-phase system

Safe cyano(nitro)methylating reagent—Michael addition of cyano-aci-nitroacetate leading to δ-functionalized α-nitronitriles

“…Although the reaction proceeded efficiently in either nonpolar benzene or polar ethanol, the ratio of 5a/6aa was not affected by the polarity of the solvent (entries 2-3). Chloroform was found to be somewhat effective for the predominant single addition; however, all attempts for complete synthesis of the single Michael adduct 5a failed (entries [5][6][7][8]. To our great surprise, the single Michael adduct 5a was obtained as a sole product when 2A was used as a base (entry 9).…”

“…4 Semenov overcame these drawbacks by using a two phase system, by which NAN is prepared in good yield. 5 However, Thomas recently alerted on the explosive property of the NAN. 6 In this context, the development of a safe alternative cyano(nitro)methylation agent is required.…”

Nitroacetonitrile as a versatile precursor in energetic materials synthesis

“…43 Another purication option reported is to decolorize the oil with activated charcoal, then turn the compound into a salt with gaseous ammonia before acidifying and extracting into ether. 45 In 1994, Kislyi et al 46 reported an alternate method for the synthesis of nitroacetonitrile from nitrocyanoacetone with a yield of 70-85% via deacylation. Nitrocyanoacetone was prepared by the nitration of cyanoacetone with a sulfuric acid/ nitric acid mixture in chloroform (Scheme 6).…”

“…Nitroacetonitrile was then isolated as a residue via extraction and evaporation of the organic solvent. 46…”

Chemistry of 2-aryl-1-cyano-1-nitroethenes. Part I. Synthesis and physical properties

“…Therefore, attempts to purify it via vapour distillation are potentially very dangerous [13]. Kislyi and coworkers [19] have described an alternative, more effective synthetic way for preparing NAN. In this approach, NAN is synthesized according to a two-stage procedure: (i) nitration of cyanoacetone (CA) in a two-phase system, and next, (ii) deacylation of the nitrocarbonyl intermediate product (NCA).…”