Thermal and photobromination of naphthalene and derivatives have been studied. Several hexabromo- (12, 13, 16 and 17), and tetrabromotetralin derivatives (23, 24, and 25) have been obtained as the major products, besides bromonaphthalene derivatives. Base-promoted elimination reactions of 12, 13, 16 and 17 provided di- (8) tri- (10) and tetrabromo-naphthalenes (22). A convenient method was developed for the synthesis of 1,3-dibromonaphthalene (26) starting from (24). The structures of these products were determined by H-1-,C-13- NMR data and X-ray structural analysis. (C) 1999 Elsevier Science Ltd. All rights reserved.