DFT investigation of the thermodynamics and mechanism of electrophilic chlorination and iodination of arenes.

Quantum chemical calculations at the B3LYP/6-311G level have been carried out in order to investigate the reaction mechanisms of the iodination of benzene and its monosubstituted derivatives with ICl, I(+), I (3) (+) and reagents containing N-I and O-I bonds as the iodinating agents. The results are compared with those obtained for chlorination by Cl(+) and Cl(2), both in the gas phase and in methanol solution using the PCM solvent model. We have also used the MP2/DGDZVP level of theory and the IEFPCM model to perform comparisons in a few cases.

Unusually stable, versatile, and pure arenediazonium tosylates: their preparation, structures, and synthetic applicability.

A new, simple, and effective method for the diazotization of a wide range of arylamines has been developed by using a polymer-supported diazotization agent in the presence of p-toluenesulfonic acid. Various pure arenediazonium tosylates with unusual stabilities can be easily prepared by this method. As a result, these salts are useful and versatile substrates for subsequent transformations, such as halogenation and Heck-type reactions.