Trinitrobenzene, catalysis

That the formation of molecular complexes (especially EDA complexes) can catalyse the decomposition of the cr-adduct has been discussed in Section n.E. Another possibility is that the substrate and catalyst (nucleophile or added base) form a complex which is then attacked by a new molecule of the nucleophile in this context catalysis need no longer be associated with proton removal. Thus, Ryzhakov and collaborators183 have recently shown that the N-oxides of 4-chloropyridine and 4-chloroquinoline act as jt-donors toward tetracyanoethylene and that the reactions of these substrates with pyridine and quinoline are strongly catalysed by the jr-acceptor. Similarly, the formation of a Meisenheimer complex between 1,3,5-trinitrobenzene and l,8-diazabicyclo[5,4,0]undec-7-ene in toluene has been assumed to take place via an association complex to explain the observed second-order in tertiary amine184. 

TNT that resides in aerobic environments at the surface of the soil is often degraded by photocatalyzed oxidation of the methyl carbon. This oxidation is probably a multistep process by which the methyl group is initially oxidized to an alcohol, then to an aldehyde, and finally to a carboxylic acid. Decarboxylation of the resultant product yields trinitrobenzene. Evidence for this pathway was supplied by Spanggord et al. [29], who reported formation of trinitrobenzaldehyde and trinitrobenzoic acid during the degradation of TNT to trinitrobenzene. It has been reported that oxidation of the methyl group of TNT is mediated by surface catalysis on soil minerals [30], by ozonation [31], and by the action of sunlight [29], At sites where the TNT contamination is localized to the soil surface, the concentration of trinitrobenzene may often exceed that of TNT [32],... 

Woodward " suggested the possibility of catalyzing the diene synthesis with N,N-diethylaniline and 1,3,5-trinitrobenzene although no experimental details were given. Others suggested acid catalysis but the increases in rate were small.Yates and Eaton showed that an adduct of 2,3-dimethyl-naphthalene 200 with maleic anhydride could be obtained in 4 h at room... 

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