Preparation of Highly Strained Aromatic Chlorocarbons. I. A Powerful Nuclear Chlorinating Agent. Relevant Reactivity Phenomena Traceable to Molecular Strain

摘要

The preparation of perchlorotoluene and perchloro-p-xylene was effected starting from 2,3,4,5-tetrachloro-1-trichloromethylbenzene and 1,4-bistrichloromethylbenzene, respectively, by means of a powerful nuclear chlorinating agent. 1,3,5-Tristrichloromethylbenzene was inert under the same conditions. Chlorination of 2,4,6-trichloromesitylene with chlorine and white light gave 2,4,6-trichloro-1,3,5-trisdichloromethylbenzene and products of chlorinolysis, no perchloromesitylene being isolated. Perchlorotoluene and perchloro-p-xylene readily underwent chlorinolysis under photochlorination conditions. 2,3,5,6-Tetrachloro-1-trichloromethylbenzene, 2,5-dichloro-1,4-bistrichloromethylbenzene and 2,3,5,6-tetrachlorobenzoic acid, are also reported for first time. Some significant results related with the preparation and stability of these chlorocarbons are explained on the basis of steric strain and distortion. (Author)