Abstract
Grignard reagents cleave the oxirane ring of 2,7-epoxydiisophoran-1-ol producing diisophor-7-ene-1,2-diol, the formulation of which is in accord with its13C-nmr spectrum, and its further reactions. It yields a 1,2-cyclic sulphite ester, a 7,8-epoxide, and is converted into 1-acetoxydiisophora-2,7-diene by acetic anhydride, and into diisophor-2(7)-en-1-ol by successive dehydration and hydrogenation. Its allylic hydroxylation by selenium dioxide is attended by dehydration, producing moderate yields of diisophora-2,7-diene-1,6-diol.
Zusammenfassung
2,7-Epoxydiisophoran-1-ol wird vonGrignard-Verbindungen unter Spaltung des Oxiranringes in Diisophor-7-en-1,2-diol umgewandelt, dessen Struktur durch sein13C-Kernresonanz-Spektrum und seine weiteren Umsetzungen bewiesen wird: Es bildet einen cyklischen 1,2-Sulphit-Ester, ein 7,8-Epoxyd, und wird von Essigsäureanhydrid in 1-Acetoxydiisophora-2,7-dien sowie durch aufeinanderfolgende Wasserabspaltung und katalytische Hydrierung in Diisophor-2(7)-en-1-ol umgewandelt. Hydroxylierung in Allyl-Stellung durch Selendioxyd ergibt unter gleichzeitiger Wasserabspaltung geringe Ausbeuten von Diisophora-2,7-dien-1,6-diol.
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Allen, A.A., Kurzer, F. Diisophorone and related compounds. Part 15 2,7-Epoxydiisophoranes: Oxirane cleavage byGrignard reagents. Monatsh Chem 116, 777–787 (1985). https://doi.org/10.1007/BF00809155
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DOI: https://doi.org/10.1007/BF00809155