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Synthesis of mesocyclic and macrocyclic polythioethers using the cesium dithiolate technique

1990; Wiley; Volume: 1; Issue: 5 Linguagem: Inglês

10.1002/hc.520010506

1098-1071

William N. Setzer, Shahrara Afshar, Norman Burns, Lucille Ferrante, Amy M. Hester, Edward J. Meehan, Gregory J. Grant, Saju M. Isaac, Christopher P. Laudeman, Charles Lewis, Donald G. VanDerveer,

Fluorine in Organic Chemistry

Abstract The mesocyclic trithioethers, 1,4,7‐trithiacyclodecane, 1,4,7‐trithiacycloundecane, 1,4,8‐trithiacycloundecane, and 1,5,9‐trithiacyclododecane; the mesocyclic trithioether ketones, 1,4,7‐trithiacyclodecan‐9‐one; 1,4,8‐trithiacycloundecan‐6‐one, and 1,5,9‐trithiacyclododecan‐3‐one; and the mesocyclic trithioether alcohols, 1,4,7‐trithiacyclodecan‐9‐ol, 1,4,8‐trithiacycloundecan‐6‐ol, and 1,5,9‐trithiacyclododecan‐3‐ol, have been synthesized using the cesium dithiolate technique. In some cases, the corresponding macrocyclic hexathioether was isolated from the reaction mixture in addition to the mesocyclic trithioether; 1,4,7,11,14,17‐hexathiacycloeicosane, 1,4,7,11,14,17‐hexathiacycloeicosan‐9,19‐dione, 1,4,7,12,15,18‐hexathiacyclodocosane, and 1,5,9,13,17,21‐hexathiacyclotetracosane. Single‐crystal X‐ray structures have been determined for 1,5,9‐trithiacyclododecan‐3‐ol and 1,4,7,12,15,18‐hexathiacyclodocosane. For 1,5,9‐trithiacyclododecane‐3‐ol, the compound crystallizes in the monoclinic space group, C2/c, with a = 10.5926( 9 ) Å, b = 15.582(2) Å, c = 13.6015(8) Å, β = 98.186(6) 0 , Z = 8, and R = 0.038. The macrocycle, 1,4,7,12,15,18‐hexathiacyclodocosane, crystallizes in the orthorhombic space group, Pbca, with a = 21.406(5) Å, b = 9.810(2) Å, c = 10.225(2) Å, Z = 4, and R = 0.020.