Improved Halogenation of Methyl Aromatics and Methyl Heteroaromatics: Unexpected Reactivity of Tetrahalogeno-diphenylglycolurils

1,3,4,6-Tetrachloro (TCDGU) and 1, 3,4,6-tetrabromo-3 alpha,6 alpha-diphenylglycolurils smooth halogen oxidizers have been exploited in a new direction as reagents for free radical substitution toward some N-halosuccinimide nonreactive bisheterocycles. An unexpected selectivity and reactivity were observed with methyl benzenes, methyl heterocycles, and methyl-bis-heterocycles of interest. A chemometric study has been performed to optimize five independent factors of the chlorination reaction with TCDGU. The predictive model was established either for the halogenation conversion and the ratio of monochlorination. (C) 2016 Wiley Periodicals, Inc.