Macrocycles with 1,2-dicyano-1,2-dithioethene units |
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Authors: | Anke Spannenberg Dirk Abeln Jürgen Kopf Hans-Joachim Drexler Hans-Jürgen Holdt |
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Affiliation: | 1. Abteilung für Anorganische Chemie, Fachbereich Chemie der Universit?t , Buchbinderstr. 9, D-18051, Rostock, Germany;2. Institut für Anorganische und Angewandte Chemie der Universit?t , Martin-Luther-King-Platz 6, D-20146, Hamburg, Germany |
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Abstract: | Abstract 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 the cyclization of (Z)-disodium-1,2-dicyanoethene-1,2-dithiolate (Z)-3 with ω,ω'-dibromoalkanes BrCH2CH2(CH2)nCH2Br (n = 0;1;2;3) on refluxing in dioxane in yields up to 15%. By reaction of the dithiolate (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, respectively, were formed in addition to the (Z,Z)-isomers. The (E,E)- and (Z,E)-isomers are photochemically convertable to the corresponding themodynamically more stable (Z,Z)-isomers by irradiation with UV-light. The (E,E)-isomers can be synthesized in a straightforward manner using the (E)-disodium-1,2-dicyanoethene-1,2-dithiolate (E)-3. Crystal structures of (Z,Z)-5, (Z,Z)-6, (E,E)-6, (Z,E)-7 and (E,E)-7 are reported. |
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