Disposal of Dangerous Chemicals in Urban Areas and Mega Cities by Ian Barnes & Krzysztof J. Rudziński

Author:Ian Barnes & Krzysztof J. Rudziński
Language: eng
Format: epub
Publisher: Springer Netherlands, Dordrecht

The relative energies of the intermediates, IM1-Y, and TS1-Y are tabulated in Table 13.1. For m-cresol, the three IM1-Y structures have almost the same energies whereas there is an energy difference for the two IM1-Y structures for o-cresol. The transition states TS1-Y are best stabilized if the NO2 has been added ortho to the –OH group (e.g. at C2 or C6 position). For m-cresol the transition state, TS1-6, is better stabilized than TS1-2, this may indicate that addition to C6 is preferential compared to C2 addition. The energy barrier associated with the 1,4-elimination of HNO3 from carbon atoms located at opposite side of the carbon ring like IM1-4 is greater than the one associated with the 1,2-elimination of HNO3 from adjacent carbon atoms like IM1-2 or IM1-6. It is more favorable for 1,2-elimnation than 1,4-eliminations.

The following methyl-nitrophenol isomers are formed in the NO3 initiated reaction; 4-methyl-2-nitrophenol for p-cresol, and 5-methyl-2-nitrophenol (major product), 3-methyl-2-nitrophenol and 3-methyl-4-nitrophenol for m-cresol, and 2-methyl-4-nitrophenol for o-cresol.

The rate determining step for the addition-elimination reaction channel is the addition of NO3 to the aromatic ring. The energies of the transition states describing the addition are 7 kcal/mol or less above the individual reactants.

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