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Diisophorone and related compounds. Part 19 Synthesis and reactions of 6,8-dibromodiisophorones

Diisophoron und verwandte Verbindungen, 19. Mitt.: Synthese und Reaktionen von 6,8-Dibromdiisophoronen

  • Organische Chemie Und Biochemie
  • Published:
Monatshefte für Chemie / Chemical Monthly Aims and scope Submit manuscript

Abstract

Novel 6,8-dibromo-derivatives of diisophor-2(7)-en-1-ol-3-one and the corresponding 1-carboxylic acid methyl ester are readily accessible by the action of 2 mol of N-bromosuccinimide on the respective parent compounds. Treatment with alkali converts the 6,8-dibromo-ketol, by a simultaneous 8-substitution and ring A-aromatisation, into 6-methyl-5-nordiisophora-2(7),3,5-triene-1,3,8-triol; acetolysis and methanolysis produce the corresponding 8-acetoxy- and 8-methoxy-compounds. The 6,8-dibromo-1-carboxylic acid reacts analogously, with the added option of 1,3-lactone formation. The assigned13C-nmr spectra and fragmentation patterns of the new compounds are in accord with their proposed formulation.

Zusammenfassung

Neuartige 6,8-Dibrom-Abkömmlinge des Diisophor-2(7)-en-1-ol-3-ons und der entsprechenden 1-Carbonsäure (als Methylester) sind durch Einwirkung von 2 mol N-Bromsuccinimid auf die betreffende Grundverbindung leicht zugänglich. Bei der Umsetzung des 6,8-Dibromketols mit Alkalien entsteht 6-Methyl-5-nordiisophora-2(7),3,5-trien-1,3,8-triol, unter gleichzeitiger 8-Substituierung und Ring-A-Aromatisierung. Acetolyse und Methanolyse ergeben die entsprechenden 8-Acetoxy- und 8-Methoxy-Verbindungen. Die 6,8-Dibrom-1-carbonsäure reagiert analog, mit weiterer Möglichkeit zur 1,3-Lacton-Bildung. Die13C-Kernresonanz-und Massenspektren der neuen Verbindungen stehen mit den Strukturzuordnungen im Einklang.

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Authors and Affiliations

  1. Royal Free Hospital School of Medicine, University of London, NW3 2PF, London, England

    Frederick Kurzer, John B. O. Mitchell & Jayantilal N. Patel

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  1. Frederick Kurzer
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  2. John B. O. Mitchell
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  3. Jayantilal N. Patel
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Kurzer, F., Mitchell, J.B.O. & Patel, J.N. Diisophorone and related compounds. Part 19 Synthesis and reactions of 6,8-dibromodiisophorones. Monatsh Chem 119, 195–213 (1988). https://doi.org/10.1007/BF00809594

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