PARTIALLY FLUORINATED MACROCYCLES - SYNTHESIS OF THE TETRAFLUORO ANALOG OF THE [2S.2O.2O]-CRYPTAND AND THE CRYSTAL-STRUCTURE OF THE SODIUM COMPLEX

Tetrafluoro-1,2-bis(chlorosulfenyl)ethane is used for the synthesis of two fluorine containing macrocycles. The insertion of ethylene into the S-Cl band, followed by an exchange of Cl against I gives 1,8-diiodo-3,6-dithia-4,4,5,5-tetrafluorooctane in two steps (overall yield 75%). This compound has been cyclized with 1,8-diamino-3,6-dioxaoctane to produce 1,4-dithia-7,16-diaza-10,13-dioxa-2,2,3,3-tetrafluorocyclooctadecane with a 30% yield, which on further reaction with 1,8-diiodo-3,6-dioxaoctane gives the cryptand 1,10-diaza-4,7,13,16-tetraoxa-21- 24-dithia-22,22,23,23-tetrafluorobicyclo[8.8.8]hexacosane, which is the fluorinated analogue of the [2S.2O.2O]- cryptand. The effect of the complexation of alkaline metal ions on the F-19 NMR shifts has been investigated. The solid state structure of the sodium complex of the fluorocryptand is reported.