Spectroscopic Studies of Naphthol Compounds. Part VII

Semi-Rigid Bis-Phosphane Ligands for Metallamacrocycle Formation

“…For the synthesis of DPPN 4 (Scheme ), 2,7‐dihydroxynaphthalene was alkylated with allyl bromide to give bis‐allyl ether 6 by a modification of the literature procedure. Addition of 18‐crown‐6 to the reaction mixture, and improved purification methods, enabled us to improve the published yield of 45% crude14 or 27% pure15 to a relatively good 59% of recrystallised product. Ultraviolet irradiation of bis‐ether 6 and diphenylphosphane in the absence of solvent gave the bis‐phosphane DPPN ( 4 ) in an overall yield for this two‐step synthesis of 41%.…”

Participation of halogen atoms in hydrogen transfer between remote positions in gas‐phase ionized isomeric haloresorcinols

“…A hydrogen atom is transferred from a hydroxy group to an adjacent halogen (Cl, Br or I) atom in the molecular cations of various 2-haloresorcinols obtained by electron ionization. This hydrogen migration followed by a subsequent transfer of the hydrogen atom from the halogen to the other hydroxy group gives rise to the highly specific elimination of H,O from resorcinols substituted by a halogen at C (2). In addition to the interesting mechanistic aspects of this sequential hydrogen migration involving one halogen and two oxygen atoms, these results may be of diagnostic importance in the differentiation of isomeric substituted resorcinols.…”

Synthesis of 3,5- and 3,6-Linked Calix[n]naphthalenes

“…Thus, 1,8-dialkyl derivatives such as 11 and 12 were explored. While bis-lactones such as 11 were too electronically deactivated for standard condensation reactions, the 1,8-bis-allyl compound 12 initially appeared to be attractive. Base-catalyzed reaction of compound 12 with paraformaldehyde in refluxing xylene resulted in the formation of a highly insoluble material from which no structural elucidation was possible.…”