Electrochemical synthesis of geminal azidonitro compounds

Electrooxidative coupling of salts of nitro compounds with halide, nitrite, cyanide, and phenylsulfinate anions

“…1,2 This method using predominantly chemical oxidants (Cl 2 , Br 2 , I 2 , AgNO 3 , K 3 Fe(CN) 6 , N halosuccinimides, (NH 4 ) 2 S 2 O 8 , and others) gave geminal nitrohalides, 3-10 nitroazides, 11-14 dinitro compounds, 15-18 nitro nitriles, 17,18 nitrosulfones, 7,17, 19 and nitroimidazoles. 20 Only dinitro compounds and nitroazides were synthe sized by electrochemical oxidation, 21-25 although, as shown by our work on the electrosynthesis of geminal azidonitro compounds, 25 this variant of preparation of α substituted nitro compounds have substantial advan tages over traditional chemical methods because excess oxidant can be replaced by ecologically pure electric cur rent. Therefore, it is undoubtedly interesting and urgent to study the electrooxidative coupling of salts of nitro compounds with inorganic and organic anions for the development of methods of electrosynthesis of nitro com pounds substituted in the α position by different func tional groups.…”

“…As in the previously described case 25 of coupling of nitro compound salts with azide anions, the study was carried out in two phase me dia, viz., CH 2 Cl 2 -aqueous solutions of NaCl, NaBr, NaI, NaNO 2 , NaCN, and PhSO 2 Na in a volume ratio of 2 : 1, under both undivided (UDE) and divided electrolysis (DE) conditions using 0.1 M aqueous solutions of NaOH or H 2 SO 4 as catholytes. An advantage of the two phase system is a possibility to extract the coupling products into the organic phase during electrolysis.…”

Electrochemical Synthesis of High-Nitrogen Materials and Energetic Materials

“…125 In 2004, Nikishin et al investigated the contribution of the azidyl radical (62) within the mechanism of electrochemical azido functionalization. 130 They proposed that sodium azide is selectively oxidized due to its lower oxidation potential relative to the nitro-functionalized alkyl substrates. This hypothesis was confirmed due to the lack of dinitro compounds that would have been formed from the dimerization of electrogenerated αnitroalkyl radicals.…”

“…In 2004, Nikishin et al investigated the contribution of the azidyl radical ( 62 ) within the mechanism of electrochemical azido functionalization . They proposed that sodium azide is selectively oxidized due to its lower oxidation potential relative to the nitro-functionalized alkyl substrates.…”

Synthesis of heterocyclic geminal nitro azides

“…The list of the described α nitro azides is limited and does not pro vide insight into the possibility of their synthesis in the series of heterocycles. [4][5][6][7][8][9] The main method for the preparation of α nitro azides consists of oxidative coupling of the azide anion with nitroalkane salts. The reaction is performed in an alkaline medium in the excess of azide under the conditions of electrochemical 4,6,9 and chemical oxidation.…”