The Chemistry of Hydrochalcogenides

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The synthesis of triptycene-9-selenoselenenic acid (TripSeSeH;Trip denotes 9-triptycyl hereafter) was investigated.1.Synthesis of diselenides, TripSeSeC(O)R.1.1.The reaction of Se-9-triptycyl triptycene-9-selenoseleninate [TripSe(O)SeTrip] with selenocarboxylic acids [RC(O)SeH] yielded the desired TripSeSeC(O)R in high yields. p-Tolyl and benzyl groups were employed as the substituent R.1.2.Selenol, TripSeH, was treated with a base, and the resulting TripSe^-was allowed to react with elemental selenium, followed by quenching the mixture with methyl iodide to give the corresponding diselenide (TripSeSeMe). This result indicated the formation of TripSeSe. When the mixture was quenched with acid, TripSeH was recovered. Using elemental sulfur, instead of selenium, led to the formation of TripSeSH in 15% yield. Diselenides, TripSeSe(O)-p-Tol and TripSeSeC(O)Me were prepared by quenching the mixture with benzoyl chloride and acetyl chloride, respectively.2.Hydrolysis of TripSeSeC(O)RHydrolysis of TripSeSeC(O)-p-Tol was carried out under acidic or basic conditions to give the selenol (TripSeH) and the triselenide (TripSeSeSeTrip) as the main products. Hydrolysis of TripSeSeC(O)Me with perchloric acid in a mixed solvent of dichloromethane and ethanol at 40℃ gave a similar mixture of TripSeH and TripSeSeSeTrip in a ration of 1:1. TripSeSeSeTrip would be formed by a dimerization of intermediary generated TripSeSeH accompanying with elimination of H_2Se. The formation of TripSeH suggests the deselenation of TripSeSeH.