A priori selection of shape-selective zeolite catalysts for the synthesis of 2,6-dimethylnaphthalene

Modeling tools based on molecular mechanics and molecular dynamics were used for selecting shape-selective zeolite catalysts for the synthesis of 2,6-dimethylnapthalene (2,6-DMN) through the alkylation of naphthalene (NAPH) or via isonterization of other DMN isomers. A number of medium- (MFI and EUO) and large-pore zeolites (*BEA, MOR, MAZ, FAU, LTL, OFF, and MTW) were considered and for each of them the minimum energy pathways for the diffusion of naphthalene, 1- and 2-methyinapthalene (MNs), and 1,5-, 1,6-, 2,6-, and 2,7-dimethylnapthalene (DMNs) were computed. The results of the simulations indicated that the diffusion of MNs and DMNs isomers in the medium-pore zeolites is impeded by high-energy barriers, leading to the conclusion that this kind of structure can be used neither in the isomerization nor in the alkylation reaction. In contrast, large-pore zeolites are more promising though their behavior strongly depends on the effective size of the pore openings. Among them, MTW was predicted to be the most promising candidate for the selective alkylation of NAPH to 2,6-DMN. In fact, the simulations indicated high-energy diffusion barriers not only for molecules bearing a -CH3 group in the alpha-position but also for the undesired 2,7-DMN molecule. Catalytic tests, performed in the presence of 1,2,4-trimethylbenzene as a solvent, confirmed the prediction since MTW gave the highest 2,6-DMN yields with a 2,6-/2,7-DMN ratio in the range 2.0-2.6, well above the thermodynamic value of I obtained with the other zeolites. The good catalytic performances of MTW were explained by the fact that, unique among the large-pore zeolites considered, this zeolite showed a better stabilization of the 1, 1 -diarylmethane intermediate molecules leading to 2-MN, 2,6-DMN, and 2,7-DMN. Their formation can be considered more probable than for those deriving from the electrophilic attack of the benzyl carbocation in the alpha-position of the naphthalene ring. (C) 2003 Elsevier Science (USA). All rights reserved.