Synthesis, structure and reactivity of β-chalcocyclohexenals: Dichalcogenides and chalcogenides

•Facile synthesis of alicyclic dichalcogenide and monochalcogenides stabilized by intramolecular Se⋯O coordination.•The strength of Se⋯O intramolecular interactions in alicyclic diselenide and their derivatives is greater than that observed for the aromatic analogues.•Pd(II) and Pt(II) metal complexes of alicyclic monotellurides isolated without the cleavage of TeC bond.

The present work describes the synthesis and characterization of a series of organochalcogen compounds derived from β-chlorocyclohexenal (27a)/β-bromocyclohexenal (27b) which are stabilized by E⋯O (E = S, Se, Te) intramolecular secondary bonding interaction (IM-SBI). Di-(2-formylcyclohex-1-ene)sulfide (21) was prepared by treating 27b with disodium sulfide. Di-(2-formylcyclohex-1-ene)diselenide (28) was obtained by reacting 27a with disodium diselenide. The reaction always produced a mixture of di-(2-formylcyclohex-1-ene)diselenide (28) and di-(2-formylcyclohex-1-ene)selenide (29). Attempts to synthesize di-(2-formylcyclohex-1-ene)ditelluride 30 by the reaction of 27b with disodium ditelluride afforded a mixture of monotellurides; 3,4,5,6,7,8-hexahydro-2H-9-telluraanthracene-1-carbaldehyde (26), di-(2-formylcyclohex-1-ene)telluride (22) and 9-hydroxy-2,3,5,6,7,8,9,9a-octahydro-1H-telluroxanthene-4-carbaldehyde (31). Reactions of 28 with halogenating reagents afforded the corresponding organylselenenyl halides; selenenyl chloride 35, selenenyl bromide 36 and selenenyl iodide 37. Tellurides 26 and 22 were used as ligands for metal complexation reactions.

Graphical abstractThe organochalcogen derivatives derived from alicyclic substrates, β-bromocyclohexenal/β-chlorocyclohexenal, show stronger Se⋯O/Te⋯O intramolecular interaction compared with the corresponding aromatic analogues.Figure optionsDownload full-size imageDownload as PowerPoint slide