Unexpected Course of Thiocyanation of 1,6‐Methano[10]annulene. Elimination of Thiocyanogen from a Diisothiocyanate

Abstract

AbstractThe isolation of the syn,syn‐adduct 5 in the reaction of 1,6‐methano[10]annulene (1) with the bulky pseudo‐halogen (SCN)2 indicates a preferred exo attack of electrophiles on 1, in spite of a possible steric interference with the methylene bridge. The formation of the unexpected isothiocyanates 4 and 5 is explained in terms of an addition‐isomerization‐elimination sequence. The novel elimination of (SCN)2 from a diisothiocyanate is investigated.