Studies on nitroacenaphthenes and nitro 1,8-dimethylnaphthalenes

Webb, B. C. (1975) Studies on nitroacenaphthenes and nitro 1,8-dimethylnaphthalenes. (PhD thesis), Kingston Polytechnic, .


A study has been made of the nitration of the three isomeric mononitroacenaphthenes and of the nitration of 4-ni tro-1,8-dimethyl¬naphthalene. The routes to the formation of 3,5,6,8-tetranitro¬acenaphthene, 3,4,5,6,S-pentanitroacenaphthene arid 2,4,5,7-tetranitro- 1,8-dimethylnaphthalene have been elucidated. A total of fourteen, hitherto unreported nitro-derivatives of the two parent hydrocarbons have been identified and procedures for the synthesis and isolation of twelve of these compounds have been developed. The oxidation of the higher polynitro derivatives of acenaphthene and 1,8 dimethynaphthalene has been investigated and this resulted in the production of two previously unreported polynitronaphthalic anhydrides, viz 2,4,5 trinitro-1,8-naphthalic anhydride and 2,4,5,7-tetranitro, 1,8-naphthalic anhydride. The reactions of 3,5,6,8-tetranitroacenaphthene and of 2,4,5,7-tetranitro-1,8-domethylnaphthalene with base has been studied and evidence obtained for the formation of a stable benzylic type anion. Base catylised coupling of 4-nitro-1.8-dimethylnaphalene has been shown to yield the previously unreported 4,4-dinitro-1,1'-naphthostilbene and 4,4'-dinitro-1,2-bis (1-naphthyl)ethane. The rates of nitration in glacial acetic acid of the three nitroacenaphthenes and 4-nitro-1,8-dimethylnaphthelene have been determined relative naphthalene. The substitution pattern in nitration products has been shown to be in good agreement woth the reactivity indices calculated using Huckel and MacLachlan molecular orbital methods. The infrared, eletronic, mass and [sup]1 H-nuclear magnetic resonance spctra of the parent hydrocarbons and their nitro-derivatives have been recorded where possible and discussed in terms of steric and electronic effects. The kinetics of the thermal decomposition of the nitro-derivatives of ancenaphthene and 1,8-dimethylnaphthalene have been investigated by differential scanning calorimetry and it has been found that the simple kinetic model could not be applied successfully to these compounds

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