Cycloaddition Reactions of 7‐Benzylidenecycloocta‐1,3,5‐triene with Ethenetetracarbonitrile and 4‐Phenyl‐3H‐1,2,4‐triazole‐3,5(4H)‐dione

An (E)/(Z) mixture (3 : 2) of 7‐benzylidenecycloocta‐1,3,5‐triene ( 5 ) is obtained when 1‐benzylcycloocta‐1,3,5,7‐tetraene ( 7 ), prepared by an improved procedure, is treated with t‐BuOK in THF. Alternatively, a ca. 9 : 1 mixture (E)/(Z)‐ 5 can be prepared in a Wittig reaction involving benzaldehyde and cycloocta‐2,4,6‐trien‐1‐ylidenetriphenylphoshorane ( 9 ). Treatment of (E)/(Z)‐ 5 88 : 12 with ethenetetracarbonitrile (TCNE) gave a complex mixture of products, from which seven mono‐adducts and two bis‐adducts were isolated (Sect. 2.2.1). Of the mono‐adducts, four are π4+π2 adducts: two ((E)‐ and (Z)‐isomers) are derived from valence tautomers of the two isomers of (E)/(Z)‐ 5 , while it is tentatively suggested that the other two (again (E)‐ and (Z)‐isomers) are formed from the intermediacy of a pentadienyl zwitterion (Sect. 2.3). The remaining three mono‐adducts, two of which are epimers, are π8+π2 adducts. It is suggested that they are derived from the intermediacy of homotropylium zwitterions (Sect. 2.3). For the two bis‐adducts, it is postulated that they are derived from an initial π2+π2 cycloaddition involving the homotropylium zwitterions followed by π4+π2 cycloaddition to the valence tautomer of each of the π2+π2 cycloadducts. With 4‐phenyl‐3H‐1,2,4‐triazole‐3,5(4H)‐dione ( 6 ), (E)/(Z)‐ 5 91 : 9 yielded two π4+π2 cycloadducts ((E)‐ and (Z)‐isomers) as well as two epimeric π8+π2 cycloadducts (Sect. 2.2.2). The intermediacy of pentadienyl (tentative suggestion) and homotropylium zwitterions accounts for the formation of the products (Sect. 2.3).