MACROCYCLES WITH 1,2-DICYANO-1,2-DITHIOETHENE UNITS

The new unsaturated macrocyclic tetrathioethers (Z,Z)-4 (n = 0), (Z,Z) -5 (n = 1), (Z,Z)-6 (n = 2) and (Z,Z)-7 (n = 3) were synthesized by th e cyclization of (Z)-disodium-1,2-dicyanoethene-1,2-dithiolate (Z)-3 w ith omega,omega'-dibromoalkanes BrCH2CH2(CH2)(n)CH2Br (n = 0;1;2;3) on refluxing in dioxane in yields up to 15%. By reaction of the dithiola te (Z)-3 with 1,3-dibromopropane the unsaturated hexathioether (Z,Z,Z) -6 was also obtained. By the cyclization of dithiolate (Z)-3 with 1,5- dibromopentane and 1,6 dibromohexane the (Z,E)- and (E,E)-isomers, res pectively, were formed in addition to the (Z,Z)-isomers. The (E,E)- an d (Z,E)-isomers are photochemically convertable to the corresponding t hemodynamically more stable (Z,Z)-isomers by irradiation with UV-light . The (E,E)-isomers can be synthesized in straightforward manner using the (E)-disodium-1,2-dicyanoethene-1,2-dithiolate (E)-3. Crystal stru ctures of (Z,Z)-5, (Z,Z)-6, (E,E)-6, (Z,E)-7 and (E,E)-7 are reported.