Synthesis of diazahexathia-24-crown-8 derivatives and structures of Ag+ complexes

Abstract

Diazahexathia-24-crown-8 (2) has been isolated from the reaction mixture during the preparation of monoazatrithia-12-crown-4 (1). When N-Boc protected bis(2-chloroethyl)amine was employed as a starting material, N-Boc protected monoazatrithia-12-crown-4 (3) and N-Boc protected diazahexathia-24-crown-4 (4) were separated easily. Double-armed diazahexathia-24-crown-8 having two 3′,5′-dichlorobenzyl groups (5a) or two 2-phenylethyl groups (5b) were also prepared using reductive amination. The stoichiometry and detailed structures of the Ag⁺ complexes with 5a and 5b were investigated by ¹H NMR titration experiments and X-ray crystallography.