Methylenediamines oxidation

Hydrogenation, of gallic add with rhodium-alumina catalyst, 43, 62 of resorcinol to dihydroresorcinol, 41,56 Hydrogen peroxide, and formic acid, with indene, 41, 53 in oxidation of benzoic add to peroxy-benzoic add, 43, 93 in oxidation of ieri-butyl alcohol to a,a/r, a -tetramcthyltetra-methylene glycol, 40, 90 in oxidation of teri-butylamine to a,<, a, a -tetramethyltetra-methylenediamine, 40, 92 in oxidation of Crystal Violet, 41, 2, 3—4... 

The nitrolysis of tertiary amines in the form of fert-butylamines and methylenediamines has been used to synthesize numerous polynitramine-based energetic materials. In these reactions one of the N-C bonds is cleaved to generate a secondary nitramine and an alcohol the latter is usually 0-nitrated or oxidized under the reaction conditions (Equation 5.15). The ease in which nitrolysis occurs is related to the stability of the expelled alkyl cation. Consequently, the fert-butyl group and the iminium cation from methylenediamines are excellent leaving groups. 

Adiponitrile is an important intermediate for the manufacture of hexa-methylenediamine (Section 3.4), which, together with adipic acid, is used to produce nylon 6,6. Although adiponitrile is still largely produced from adipic acid, obtained by vapour phase oxidation of cyclohexane (Section 2.2), it is also manufactured from butadiene by DuPont on the basis of the process first patented in 1970 (Equations 24-26). Conversion is 99% with >90% selectivity to adiponitrile. 

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