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Di-isophorone and related compounds. Part 7. Syntheses and properties of 1-hydroxydi-isophor-2(7)-ene-3,4-dione

Di-isophoron und verwandte Verbindungen, 7. Mitt. Synthesen und Eigenschaften von 1-Hydroxy-di-isophor-2(7)-en-3,4-dion

  • Organic Chemistry and Biochemistry
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Abstract

1-Hydroxydi-isophor-2(7)-ene-3,4-dione (4), the α-diketone derived from the parent di-isophorone, is obtained by several routes. Its formation by the hydrogenation of the corresponding 2,7-epoxide3 confirms its assigned structure. The action of alkali on 4-substituted 8-bromodi-isophor-2(7)-en-3-ones yields, presumably by a successive bimolecular (SN2″) substitution and hydrolysis, the 4,4-dihydroxy-precursor, from which the 3,4-diketone4 arises by loss of water. In yet another approach,4 is produced by the hydrolysis of its 4-monohydrazone, which is independently accessible from 8-bromo-1-hydroxydi-isophor-2(7)-en-3-one (8). In acidic media, the yellow diketone4 enolises to the stable isolable colourless 1,3-dihydroxydi-isophora-2,7-dien-4-one (19); the action of alkali reverses the process. Both forms of the compound yield the same 1-acyl-derivatives and 4-hydrazones.

Zusammenfassung

1-Hydroxydi-isophor-2(7)-en-3,4-dion (4), das vom Grundkörper Di-isophoron abgeleitete α-Diketon, ist auf verschiedene Weise erhältlich. Seine Bildung mittels katalytischer Hydrierung des entsprechenden 2,7-epoxyds3 sichert seine Struktur. Es entsteht ferner durch Einwirkung von Alkalien auf 4-substituierte 8-Bromdi-isophor-2(7)-en-3-one, wahrscheinlich über eine bimolekulare Substitution (SN2″) und Hydrolyse, und darauffolgende Wasserabspaltung aus den intermediären 4,4-Dihydroxy-Verbindungen. Weiters erhält man das 3,4-Diketon4 durch Hydrolyse seines 4-Hydrazons, welches seinerseits unabhängig aus 8-Brom-1-hydroxydi-isophor-2(7)-en-3-on (8) darstellbar ist. Im sauren Milieu verwandelt sich das gelbe 3,4-Diketon zum farblosen, isolierbaren 1,3-Dihydroxydi-isophor-2,7-dien-4-on (19); diese Enolisierung wird unter dem Einfluß von Alkalien umgekehrt. Beide tautomeren Formen ergeben identische 1-Acyl-Derivate und 4-Hydrazone.

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Authors and Affiliations

  1. Royal Free Hospital School of Medicine, University of London, W.C.1., London, England

    Frederick Kurzer & Alan R. Morgan

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  1. Frederick Kurzer
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  2. Alan R. Morgan
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Part 6:Davies, P. R., Kurzer, F., Morgan, A. R. Mh. Chem.111, 1097 (1980).

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Kurzer, F., Morgan, A.R. Di-isophorone and related compounds. Part 7. Syntheses and properties of 1-hydroxydi-isophor-2(7)-ene-3,4-dione. Monatshefte für Chemie 112, 129–140 (1981). https://doi.org/10.1007/BF00906250

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