Tetrazolyl and benzisothiazolyl naphthylmethylic ethers 3 and 4(a-e) are stable crystalline compounds that can be synthesised in high yields by reaction of the corresponding naphthyl methanols (1a-e) with the derivatizing agents 2a and 2b. Experimental conditions for palladium-catalysed hydrogenolysis of ethers 3, 4, with a hydrogen donor and with molecular hydrogen, were investigated. Analysis of the structure and reactivity indicates that naphthylmethylic ethers 3 and 4 are structurally similar to the corresponding benzyloxyderivatives around the ether bond but exhibit different reactivity. Structural analysis for these compounds is based on crystallographic structure determinations, for 5-(2-naphthylmethoxy)-1-phenyltetrazole (3a) and 3-(2-naphthylmethoxy)- 1,2-benzisothiazole 1, 1-dioxide (4a), and molecular orbital DFr(133LYP)/6-311G(d) calculations, for all ethers. It can be concluded from this investigation that 5-chloro-1-phenyttetrazole 2a acts as a better derivatizing agent for naphthyl methanols than 3-chloro-1,2-benzisothiazole-11-dioxide 2b, this contrasting with what has been observed with phenols, allylic and benzylic alcohols. (c) 2005 Elsevier B.V. All rights reserved.