Nitroalkanes mineral acids

The Nef reaction of primary nitro compounds gives aldehydes or carboxylic acids, depending on the reaction conditions. Each transformation provides an important tool in organic synthesis. Primary nitro compounds are converted into carboxylic acids with concentrated mineral acids.22 Because such harsh conditions also lead to side reactions, a milder method is required in organic synthesis. Basic phosphate-buffered KMn04 rapidly converts primary nitroalkanes into carboxylic acids in 90-99% yield (Eq. 6.13).23... 

Table 1.11 Reactions of nitroalkanes and polynitroalkanes with mineral acid ...

The original procedure for the Nef reaction involved the aqueous sulfuric acid hydrolysis of the salts (170) obtained by the treatment of primary and secondary nitroalkanes with sodium hydroxide (equation 30). In contrast, if a neutral primary nitro derivative is treated in hot concentrated mineral acid, the corresponding carboxylic acid (172) is formed via the hydroxamic acid (171 equation 31). This reaction is known as the Meyer reaction and was first described in 1873. Protonation of salts of nitroalkanes occurs preferentially at the oxygen atom to give the aci form (173 equation 32). 

When equal amount of concentrated mineral acid and primary nitroalkane react, a carboxylic acid and a hydroxylamine salt are generated, generally with yield of up to 85-90 %. When sulfuric acid reacts with nitromethane [6], products are CO and hydroxylamine sulfate. The mixture from the reaction between anhydride sulfuric acid and a primary nitroalkane at 60 °C was poured into ice-water and then... 

Primary nitroalkanes in the presence of hot concentrated mineral acids yields the carboxylic acid and hydroxylamine. Exhaustive chlorination of nitromethane under alkaline conditions yields chloropicrin (trichloronitrometh-ane, CI3CNO2). Secondary riitroparaffins, formaldehyde, and primary or secondary amines react in a Mannich-type reaction to give the Mannich base,... 

MINERAL RED (1314-41-6) An oxidizer. Decomposes above 932°F/500°C, emitting oxygen. Reacts, possibly violently, with reducing agents, powdered metals aluminum, titanium, zirconium, zinc, etc., alcohols, dichloromethylsilane, hydrazine, hydrogen trisulfide, ethers, glycols, peroxyformic acid, phosphorus, selenium oxychloride, sulfur trioxide. Incompatible with ammonium nitrate, diboron tetrafluoride, hydrazinium nitrate, hydrogen sulfide, nitroalkanes, rubidium acetylide, selenium oxychloride. Forms heat-sensitive explosive material with anilinium perchlorate. Increases the thermal and/or explosive sensitivity of... 

---