Accession Number : AD0702924

Title :   RADIATION-INDUCED NITRATION OF BENZENE WITH DINITROGEN TETROXIDE.

Descriptive Note : Technical rept.,

Corporate Author : PICATINNY ARSENAL DOVER N J

Personal Author(s) : Smetana,Andrew F. ; Castorina,Thomas C.

Report Date : MAR 1970

Pagination or Media Count : 36

Abstract : The gamma-radiation-induced nitration of benzene with dinitrogen tetroxide (N2O4) in the liquid phase at 20C yielded nitrobenzene (NB) as the major product and the isomerides of dinitrobenzene (DNB) as the minor products of radiolysis. The yield G(NB) increased with increasing concentration of N2O4 from 0.14 for 6 mole % N2O4 to 1.18 for 95 mole % N2O4 in benzene. The ratio of o- to p-DNB is the inverse of that obtained from conventional mixed acid nitration and is considered typical of radiolysis. The nitro-substitution product formations are shown to be from primary processes of radiolysis and are proposed as being derived from an intermediate specie involving an No2.C6H5H(+) pi-donor complex. The NO2 in equilibrium with the N2O4 in the liquid phase is regarded as the nitrating agent in the form of a radical as well as a nitronium ion (NO2(+)). Both water and nitrous acid as secondary products of radiolysis are suggested as anti-catalysts inhibiting the degree of the radiation-induced nitration. (Author)

Descriptors :   (*NITROBENZENES, SYNTHESIS(CHEMISTRY)), (*BENZENE, *NITRATION), (*RADIATION CHEMISTRY, NITRATION), NITROGEN OXIDES, FREE RADICALS

Subject Categories : Radiation and Nuclear Chemistry

Distribution Statement : APPROVED FOR PUBLIC RELEASE