Synthesis of polynitro compounds. Peroxydisulfuric acid oxidation of polynitroarylamines to polynitro aromatics

Sulfur and Phosphorus Peroxides

“…Peroxytrifluoromethanesulfonic acid prepared in situ from H 2 O 2 and excess trifluoromethanesulfonic acid is among the powerful oxidants known 31 . It oxidized pentanitroaniline to hexanitrobenzene in 90% yield.…”

Recent approaches to the synthesis of high explosive and energetic materials: A review

“…However, the most exciting development in this general field has been the discovery that polynitroarylamines can be oxidized to polynitroaromatics using peroxydisulphuric acid [144]. A number of previously unreported compounds such as hexanitrobenzene (HNB), pentanitrobenzene and 1,2,3,4-tetranitrobenzene have accordingly been prepared (scheme 110) [144], as well as other polycyclic derivatives (see schemes 114 and 127).…”

“…A number of previously unreported compounds such as hexanitrobenzene (HNB), pentanitrobenzene and 1,2,3,4-tetranitrobenzene have accordingly been prepared (scheme 110) [144], as well as other polycyclic derivatives (see schemes 114 and 127). The objective of this research was to prepare HNB because it was predicted to have a very high density and detonation velocity.…”

“…The objective of this research was to prepare HNB because it was predicted to have a very high density and detonation velocity. Although HNB was found to be extremely powerful and of only moderate sensitivity, its hydrolytic stability *was poor; exposure to moisture afforded trinitrophloroglucinol [144]. Polynitrobenzenes can also be prepared by oxidation of nitrobenzofurazan-l-oxides(nitrobenzofuroxans) with the related reagent monoperoxysulphuric acid (scheme 111) [145].…”

“…A typical sequence is shown in scheme 127 [167]. DIPAM has been further oxidized with peroxydisulphuric acid to 2,2',3,3',4,4',6,6'-octanitrobiphenyl (scheme 127) [144]. An area of recent interest is the synthesis of fluorinated analogues of energetic materials.…”