Shape-selective para-chlorination of phenol using sulfuryl chloride with the aid of microporous catalysts

Aluminum-pillared montmorillonite clay, and partially cation-exchanged L type zeolites, efficiently catalyze the selective para-chlorination of phenol using SO2Cl2 in 2,2,4-trimethylpentane at 25 °C. A conversion of ∼96%, a para-selectivity of ∼89%, and a para/ortho ratio of 8.0, were achieved with H+, Al3+, Na+, and K+-L zeolite. This heterogeneous zeolite-catalyzed process is the first example, which shows a pronounced shape-selectivity in the chlorination of phenol.