Alkanes, direct nitration

As you now know, aliphatic organic compounds belong to the alkane, alkene, and alkyne classes of compounds. Aliphatic explosives fall into both the open-chain and cycloaliphatic groups. The major sources of oxidizer in most aliphatic explosives are from the nitrate ester group (—ONO2) and the nitramine group (—NH—NO2). The nitrate esters are usually made by direct nitration of an... 

Alkyl nitrates are also formed by the reaction of AgN03 with alkyl bromides in an acetonitrile solvent. The drawback of this exchange reaction is that in most cases the yield is only about 60 to 80%. Dichloromethane extraction with solvent removal under reduced pressure has been employed to isolate the alkyl nitrates as pure reference compounds, as well as to synthesize the hydroxyalkyl nitrates from the hydroxyhalides. Direct nitration of the alkanes is achieved with 12% HNO3 in the presence of solid copper. This method is especially useful in preparing mixtures of alkyl nitrates from mixtures of the starting alkanes. 

The kinetics and mechanism of iV-nitration reactions have been reviewed and the nitration of alkanes with nitronium hexafluorophosphate in CH2CI2 or EtN02 has been shown to involve direct electrophilic insertion of NO2+ into C-H and C-C a-bonds. ... 

The catalytic oxidation of cyclohexane is performed in the liquid phase with air as reactant and in the presence of a catalyst. The resulting product is a mixture of alcohol and ketone (Table 1, entry 12) [19]. To limit formation of side-products (adipic, glutaric, and succinic acids) conversion is limited to 10-12 %. In a process developed by To ray a gas mixture containing HC1 and nitrosyl chloride is reacted with cyclohexane, with initiation by light, forming the oxime directly (Table 1, entry 12). The corrosiveness of the nitrosyl chloride causes massive problems, however [20]. The nitration of alkanes (Table 1, entry 13) became important in a liquid-phase reaction producing nitrocyclohexane which was further catalytically hydrated forming the oxime. 

There remains some doubt about the first step of the overall reaction in MeCN the final products are usually the A -alkylacetamides, as shown in Eq. (35). In neutral solution, at extreme anodic potentials, it is difficult to decide between direct [Eqs. (1), (2), and/or (3)] and indirect electron transfer [Eqs. (16), (17), and/or (18)]. For oxidation in MeCN-BF4 solutions the variation in potentials is best explained in terms of the direct mechanism. An indirect oxidation mechanism involving hydrogen abstraction by electrogenerated nitrate radical has recently been proposed for the electrolysis of linear alkanes in tert-BUOH/H2O mixtures containing HNO3 and saturated with O2 [25]. 

It has been demonstrated in solution phase studies that carbenium ions might be formed directly from alkanes via formal hydride abstraction, instead of via nitration followed by protodenitration. 

It has developed a series of liquid explosives with multispecies since first synthesis. According to their reaction characteristics, liquid explosives are classified into single compound liquid explosives and liquid explosive mixture. Single compound liquid explosives, such as nitrate esters, nitro alkanes, azide esters, azide alkanes, and azide nitro alcohol, consist of a single explosive liquid compound. Without any other additions, a single compound liquid explosive can be directly initiated by a detonator or flame. Its explosion strength is, sometimes, over TNT energy. 

---