A DFT study of the chemical reactivity of thiobencarb and its oxidized derivatives in aqueous phase

Abstract

In the present work, the global and local reactivity of S-(4-chlorobenzyl)- N,N-diethylthiocarbamate (TB) and its oxidized derivatives (sulfone (TBSu) and sulfoxide (TBS) were analyzed. In addition, the chemical reactivities of the dechlorinated forms of TB (DTB), TBSu (DTBSu) and TBS (DTBS) were studied. The calculations were performed at the wB97XD/6- -311++G(2d,2p) level of theory in the aqueous phase. The condensed Fukui functions indicated that for TB and DTB, the most preferred sites for donating electron in a reaction are located on the S and N atoms, while the most reactive sites for accepting electrons are associated with the aromatic ring (AR). For TBS and DTBS, the more reactive sites are located on AR, S and AR for nucleophilic, electrophilic and free radical attacks, respectively. In the case of TBSu and DTBSu, the results showed AR to be the more reactive zone for the three kinds of attacks. These last results suggest that cleavage of the C–S bond in TB, TBS and their dechlorinated forms is favored by electrophilic attacks. Additionally, the obtained results suggest that in TB, it is plausible that the cleavage of the C–N is favored on attack of this molecule by electrophiles.

Keywords

• thiobencarb
• Fukui function
• dual descriptor
• DFT