Abstract
Addition of methanolic sodium methoxide to dilute solutions of di-,tri- , or tetranitrosubstituted-naphthalenes results in the rapid formation of sigma (or Meisenheimer) complexes followed by the subsequent slower elimination of nitrite ion to form the methoxysubstituted-nitronaphthalenes as the final product. The equilibrium attainment for the formation of these sigma complexes as well as the liberation of nitrite ion from some of them has been followed using absorption spectroscopy from which rate and equilibrium data as well as thermodynamic parameters were calculated. The structures of most of the intermediate sigma complexes were deduced from pmr spectroscopic data. The stability , structure, and mechanism for the formation and decomposition of the methoxy complexes formed from 1,3-dinitronaphthaiene, 1,3,8-trinitronaphthalene, 1,4 ,5 -trinitro - naphthalene, 1,3,5,8-tetranitronaphthalene, 1 ,4,5,8-tetranitronaphthalene, and 1 ,3 ,6 ,8 -tetranitronaphthalene are discussed comparatively. It was found that the stability of the series of methoxycomplexes formed parallels the extent of electron delocalization possible and that the stability of these complexes can be predicted to a fair degree by comparing the equilibrium data of similar sigma complexes which differ only in the number and position of the nitro groups.
Hinze, Willie Lee (1974). Kinetic and NMR study of the interaction of methoxide ions with some di-, tri-, and tetra-substituted nitronaphthalenes. Doctoral dissertation, Texas A&M University. Texas A&M University. Libraries. Available electronically from
https : / /hdl .handle .net /1969 .1 /DISSERTATIONS -174684.