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.

The 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 as PowerPoint slide