Monatshefte für Chemie / Chemical Monthly

, Volume 118, Issue 8–9, pp 1039–1056 | Cite as

2-Cyclopropyliden-1,3-cycloalkandione als Zwischenstufen einer nukleophilen Substitution am Dreiring

  • Jürgen Weidner
  • Elmar Vilsmaier
  • Ralf Fries
Organische Chemie Und Biochemie

2-Cyclopropylidene-1,3-cycloalkanediones as intermediates in a nucleophilic substitution at a three membered ring

Abstract

Reaction of morpholinobicycloalkyl-dimedone4 C with various CH-acids3 leads to a substitution of theexo-dimedone unit as a consequence of a strong preference of theexo-leaving group in a bicyclic compound of type4 and5, respectively. Dimedone (3 C) as a nucleophile, however, makes theexo substitution unproductive in4 C and allows the displacement of the morpholino moiety leading to12 C. Thus compounds12 C–12 F could be obtained directly from the N,O-acetal1 and the CH-acids3 C–3 F by a twofold substitution, the isolation of the monoalkylated compounds4 not being necessary. Formation of12 C–12 F involves aMichael addition of3 C–3 F to the unstable 2-Cyclopropylidene-1,3-cycloalkanedione intermediates7 C–7 F. Cyclopentanedione3 F as a CH-acid and1 gave the enamine17 F besides12 F. The Hexahydroazepino-N,O-acetal19 in this special case was superior leading exclusively to12 F.

Keywords

Aminobicyclo[n. 1.0]alkane derivatives 2-Cyclopropylidene-1,3-cycloalkanedione intermediates Cyclopropanes, nucleophilic substitution at 

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Literatur

  1. [1]
    Vilsmaier E (1987) Aminocyclopropanes. In:Rappoport Z,Patai S (eds) The chemistry of the cyclopropylgroup. Wiley, London, im Druck (The chemistry of functional groups)Google Scholar
  2. [2]
    Vilsmaier E (1985) Bull Soc Chim Belg 94: 521Google Scholar
  3. [3]
    Vilsmaier E, Joerg K, Maas G (1984) Chem Ber 117: 2947Google Scholar
  4. [4]
    Weidner J,Nauert R,Vilsmaier E (1985) unveröffentliche Ergebnisse, Univ KaiserslauternGoogle Scholar
  5. [5]
    Vilsmaier E, Joerg K, Nauert R (1984) Chem Ber 117: 2928Google Scholar
  6. [6]
    Vilsmaier E, Joerg K (1984) Chem Ber 117: 2910Google Scholar
  7. [7]
    Vilsmaier E, Klein CM, Adam R (1984) J Chem Soc Perkin Trans 2: 23Google Scholar
  8. [8]
    Horning EC, Horning MG (1946) J Org Chem 11: 95;Hutchinson DW, Tomlinson JA (1969) Tetrahedron 25: 2531Google Scholar
  9. [9]
    Vilsmaier E, Tröger W (1979) Angew Chem 91: 860; Angew Chem Int Ed Engl 18: 798;Vilsmaier E, Tröger W, Haag G (1981) Chem Ber 114: 67Google Scholar
  10. [10]
    Vilsmaier E, Tröger W, Gewehr M (1981) Angew Chem 93: 277; Angew Chem Int Ed Engl 20: 273Google Scholar
  11. [11]
    Vilsmaier E, Kristen G (1982) Chem Ber 115: 1224Google Scholar
  12. [12]
    Vilsmaier E, Schwaben B, Joerg K (1984) Chem Ber 117: 2900Google Scholar
  13. [13]
    Vilsmaier E,Kelkel S (1983) unveröffentlichte Ergebnisse, Univ KaiserslauternGoogle Scholar
  14. [14]
    Benzing M,Vilsmaier E (1985) unveröffentlichte Ergebnisse, Univ KaiserslauternGoogle Scholar
  15. [15]
    Schuster P, Polansky OE (1968) Monatsh Chem 99: 1234Google Scholar
  16. [16]
    Kunz FJ, Margaretha P, Polansky OE (1970) Chimia 24: 165Google Scholar
  17. [17]
    Vilsmaier E, Tröger W (1982) Chem Ber 115: 1644Google Scholar
  18. [18]
    Weidner J, Vilsmaier E (1987) Monatsh Chem 118: 1057Google Scholar
  19. [19]
    Merényi F, Nilsson M (1963) Acta Chem Scand 17: 1801; (1964) ibid 18: 1368Google Scholar
  20. [20]
    Joerg K (1984) Dissertation Univ KaiserslauternGoogle Scholar
  21. [21]
    Biltz H, Wittek H (1921) Ber Dtsch Chem Ges 54: 1035Google Scholar
  22. [22]
    Eistert B, Haupter F, Schank K (1963) Liebigs Ann Chem 665: 55Google Scholar
  23. [23]
    Eistert B, Eifler W, Göth H (1968) Chem Ber 101: 2162Google Scholar
  24. [24]
    Cone EJ, Garner RH, Hayes AW (1972) J Org Chem 37: 4436Google Scholar

Copyright information

© Springer-Verlag 1987

Authors and Affiliations

  • Jürgen Weidner
    • 1
  • Elmar Vilsmaier
    • 1
  • Ralf Fries
    • 1
  1. 1.Fachbereich ChemieUniversität KaiserslauternKaiserslauternBundesrepublik Deutschland

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