Carboxylation of Alkanes with CO and

The present strategy was successfully applied to the preparation of adamantane-dicarboxylic acid, which is an interesting monomer in polymer chemistry, through a stepwise procedure (Eq. (6.24)), although the dicarboxylic acid is difficult to obtain by conventional methods. Similarly, 1,3-dimethyladamantaneand mdo-tricyclo[5.2.1.0] decane were carboxylated to the respective mono- and dicarboxylic acids. 

Nitration of lower alkanes such as methane and ethane with nitric acid or nitrogen dioxide is industrially practiced to produce nitroalkanes [146,147]. However, a major problem in current industrial nitration is that the reaction must be run at fairly high temperature (250-400 °C) because of the difficulty of obtaining C—H bond homolysis by NO2 [146]. Under such high temperatures, higher alkanes undergo not only homolysis of the C— H bonds but also cleavage of the C—C skeleton. Hence, the 

It is important that the NHPI-catalyzed nitration is conducted under air, since NO generated in the course of the reaction can be readily reoxidized to NO2 by O2. In the absence of air, the yield of nitrocydohexane decreases to 43%. After the nitration, the NHPI catalyst can be separated from the reaction mixture by simple filtration and reused repeatedly. Nitrocydohexane is easily reduced to cyclohexanone oxime. Therefore, this nitration provides an alternative practical route to cyclohexanone oxime, which is a raw material for s-caprolactam leading to nylon-6 [150, 151].  

1) Although E-caprolactam is currently produced by the reaction of cyclohexanone with hydroxylamine followed by a Beckmann rearrangement with sulfuric add, the efEdency for the production of cyclohexanone by aerobic oxidation of cyclohexane is not high. 

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A metal-free system was already established for the carboxylation of alkanes with CO and water, operating in water-acetonitrile and under acid-free conditions. The latter feature (no added acid) is common to a few other catalytic systems active for alkane hydroxylation, namely by taking advantage of a ligand bearing an acid group ( dual-role catalyst ). 

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