Novel synthesis of 1,2,4‐triazolophanes and 1,3,4‐oxadiazolophanes: A dieckmann condensation approach

Abstract

The Dieckmann condensation has been used for the first time for the syntheses of novel 1,2,4-triazolophanes and 1,3,4-oxadiazolophanes. The bis-1,3,4-oxadiazol-2-thiols 1a and 1b were reacted with ethyl bromoacetate to give the diesters 2a and 2b. Diesters 2a and 2b were treated under dry conditions with sodium methoxide in methanol to afford desired symmetrical 1,3,4-oxadiazolophanes 3a and 3b. Similarly, diesters of macrocycle precursors containing 1,2,4-triazole moiety, that is, 6a, 6b, 10, 13a, 13b, and 13c were synthesized from 5a, 5b, 9, 12a, 12b, and 12c, respectively. Dieckmann condensation of these diesters afforded symmetrical ketones 7a, 7b, 11, 14a, 14b, and 14c. Extrusion of CO 2 was observed after in situ hydrolysis of the conventional Dieckmann product during neutralization by dilute mineral acids to afford highly symmetrical ketone in good yields. Further, the ketones 14a, 14b, and 14c were converted into their respective thiones by the reaction with Lawesson's reagent. All the products were synthesized with good yields, and structures were confirmed by various spectroscopic tools and elemental analyses.