Orthoamide und Iminiumsalze, XCII. Synthese und Reaktionen von Orthoamiden aus ethinylierten Terpenderivatena

Willi Kantlehner 1 , 2 , Jochen Mezger 3 , Ralf Kreß 3  and Wolfgang Frey 3
  • 1 Institut für Angewandte Forschung, Abteilung Technische Organische Synthesechemie und Katalyseforschung (TOSKA), Hochschule Aalen, Beethovenstr. 1, D-73430 Aalen, Germany
  • 2 Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • 3 Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
Willi Kantlehner
  • Corresponding author
  • Institut für Angewandte Forschung, Abteilung Technische Organische Synthesechemie und Katalyseforschung (TOSKA), Hochschule Aalen, Beethovenstr. 1, D-73430 Aalen, Germany
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Email
  • Search for other articles:
  • degruyter.comGoogle Scholar
, Jochen Mezger
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Search for other articles:
  • degruyter.comGoogle Scholar
, Ralf Kreß
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Search for other articles:
  • degruyter.comGoogle Scholar
and Wolfgang Frey
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Search for other articles:
  • degruyter.comGoogle Scholar

Abstract

β-Ionone and camphor were ethynylated to give the alkynols 14, 16, 17 which can be transformed to the alkynolethers 5b, 5i, 5j, 5k, 5l, 5m by treatment with dimethylsulfate and chlorotrimethylsilane, respectively. From the alkynolethers 5h, 5i, 5j/5k, 5l/5m the orthoamide derivatives 4h, 4i, 4j/4k, 4l/4m can be prepared by treatment with N,N,N,N,N,N″-hexamethylguanidinium chloride (8) in the presence of sodium hydride. The orthoamides 4h, 4i react with the sulfonamide 30 under condensation yielding the N-sulfonylated acrylamidines 31, 32. From the orthoamide 4h and p-nitroaniline the propiolamidine 29 could be obtained. The orthoamides 4j/4k and 4l/4m, react with benzamidine to give the pyrimidines 33, 34, respectively. In the reaction of malonodinitrile (9a) with the orthoamides 4i and 4j/4k, mixtures of 1,1-diamino-1,3-butadienes 36, 38 and 1,3-diamino-1,3-butadienes 37 and 39 are produced, respectively. From CH2-acidic compounds as ethylcyanacetate (9b), diethyl-malonate (9c) and nitromethane (9d) and the orthoamide 4i the 1,1-diamino-1,3-butadienes 36bd were produced. The pyridone derivative 40 can be prepared from cyanoacetamide (9e) and the orthoamide 4i. The condensation of the orthoamides 4j/4k with cyanoacetamide (9e) affords a mixture of the pyrimidone 41 and the nicotinonitrile 42.

  • [1]

    G. Knobloch, S. Saur, A. R. Gentner, T. Stein, B. Hader, W. Kantlehner, Z. Naturforsch. 2016, 71b, 719.

  • [2]

    Zusammenstellung von Übersichtsartikeln unter Lit. [2] in W. Kantlehner, R. Stieglitz, M. Hauber, E. Haug, C. Regele, Prakt. Chem. 2000, 342, 256.

    • Crossref
    • Export Citation
  • [3]

    H. Weingarten, Tetrahedron 1968, 24, 2767.

  • [4]

    W. Kantlehner, R. Kreß, J. Mezger, S. Ladendorf, Z. Naturforsch. 2005, 60b, 1.

  • [5]

    Übersicht: W. Kantlehner in Science of Synthesis, Bd. 22 (Hrsg.: A. B. Charette), Georg Thieme Verlag Stuttgart, New York, 2005, S. 795.

  • [6]

    M. Kordian, H. Feist, W. Kantlehner, M. Michalik, K. Peseke, Z. Naturforsch. 2006, 61b, 406.

  • [7]

    W. Weingartner, W. Kantlehner, G. Maas, Synthesis 2011, 43, 265.

  • [8]

    K. Drandarov, W. Kantlehner, Z. Naturforsch. 2012, 67b, 699.

  • [9]

    Übersicht: W. Kantlehner in Science of Synthesis, Bd. 24 (Hrsg.: A. de Meijere), Georg Thieme Verlag, Stuttgart, 2006, S. 571.

  • [10]

    W. Kantlehner, J. Mezger, R. Stieglitz, K. Edelmann, H. Lehman, M. Vettel, R. Kreß, W. Frey, S. Ladendorf, Z. Naturforsch. 2007, 62b, 1015.

  • [11]

    L. Brandsma, Studies in Organic Chemistry 34, Preparative Acetylenic Chemistry, 2. Aufl., Elsevier, Amsterdam, Oxford, New York, Toronto, 1998, S. 91 und S. 203.

  • [12]

    M. L. Capman, M. W. Chodkiewicz, P. Cadiot, Tetrahedron. Lett. 1965, 21, 1619.

    • Crossref
    • Export Citation
  • [13]

    M. L. Capman, M. W. Chodkiewicz, P. Cadiot, Bull. Soc. Chim. Fr. 1968, 3233.

  • [14]

    Y. G. Garrat, P. L. Beaulieu, V. M. Marisset, Can. J. Chem. 1981, 59, 927.

    • Crossref
    • Export Citation
  • [15]

    E. V. Dehmlow, U. Engel, C. Woelke, J. Prakt. Chem. 1996, 338, 175.

    • Crossref
    • Export Citation
  • [16]

    W. Kantlehner, G. Simchen, J. Mezger, E. V. Stoyanov, R. Kreß, W. Frey, B. Sievers, Z. Naturforsch. 2005, 60b, 231.

  • [17]

    M. M. Midland, J. Org. Chem. 1975, 40, 2250.

  • [18]

    M. M. Midland, J. I. Loughlin, R. T. Werley, Org. Synth. Coll. 1993, 8, S. 391.

  • [19]

    S. S. Koval’skaya, N. G. Kozlov, E. A. Dikusar, Russ. J. Org. Chem. 2000, 36, 379.

  • [20]

    N. F. Bonder, S. S. Koval’skaya, R. V. Skupskaya, F. S. Pashkowski, E. A. Dikusar, N. G. Kozlov, F. A. Lakhoich, Russ. J. Org. Chem. 2001, 37, 23.

    • Crossref
    • Export Citation
  • [21]

    D. R. Brittelli, G. A. Boswell Jr., J. Org. Chem. 1981, 46, 312.

  • [22]

    D. G. Morris, A. G. Shephard, M. F. Walker, R. W. Jennison, Aust. J. Chem. 1982, 35, 1061.

    • Crossref
    • Export Citation
  • [23]

    E. Djuardi, P. Bovonsombat, E. Mc. Nelis, Tetrahedron 1994, 41, 11793.

  • [24]

    M. Kagawa, Chem. Pharm. Bull. 1959, 7, 306.

  • [25]

    M. Kagawa, Chem. Pharm. Bull. 1959, 7, 751; Chem. Abstr. 1961, 55, 24808g.

    • Crossref
    • Export Citation
  • [26]

    I. K. Swhov, K. K. Mateeva, Zh. Obshch. Khim. 1944, 14, 319; Chem. Abstr. 1945, 39, 4066.

  • [27]

    B. Görlich, G. Hildebrandt, Chem. Ber. 1958, 91, 2388.

  • [28]

    C. D. Hurd, R. E. Christ, J. Am. Chem. Soc. 1937, 59, 118.

  • [29]

    E. Cuignet, Bull. Soc. Chim. Fr. 1955, 91.

  • [30]

    W. Kantlehner, M. Hauber, E. Haug, C. Schallenmüller, C. Regele, J. Prakt. Chem. 2000, 342, 682.

    • Crossref
    • Export Citation
  • [31]

    K. Kargomard, J. C. Tardivat, J. P. Killeme, Bull. Soc. Chim. Fr. 1975, 217.

  • [32]

    W. Kantlehner, P. Speh, H. Lehmann, H.-J. Bräuner, E. Haug, W. W. Mergen, Chemiker Ztg. 1990, 114, 176.

  • [33]

    W. Kantlehner, M. Vettel, H. Lehmann, K. Edelmann, R. Stieglitz, J. Ivanov, Prak. Chem./Chemiker Ztg. 1998, 340, 408.

    • Crossref
    • Export Citation
  • [34]

    W. Kantlehner, E. Haug, R. Stieglitz, W. Frey, R. Kreß, J. Mezger, Z. Naturforsch. 2002, 57b, 399.

  • [35]

    W. Kantlehner, H.-J. Lehmann, K. Edelmann, J. Mezger, I. C. Ivanov, Appl. Catal. A 2008, 336, 148.

    • Crossref
    • Export Citation
  • [36]

    G. Hauthal, D. Schied, Z. Chem. 1969, 2, 62.

  • [37]

    W. Kantlehner, F. Wagner, H. Bredereck, Liebigs Ann. Chem. 1980, 334.

  • [38]

    S. Singh, V. Gajulapati, M. Kim, J.-I. Goo, J. K. Lee, K. Lee, C.-K. Lee, L. S. Jeong, Y. Choi, Synthesis 2016, 48, 3050.

    • Crossref
    • Export Citation
  • [39]

    R. A. Pike, R. L. Schlenk, J. Org. Chem, 1962 , 27, 2190.

  • [40]

    G. M. Sheldrick, Acta Crystallogr. 1990, A46, 467.

  • [41]

    G. M. Sheldrick, Acta Crystallogr. 2008, A64, 112.

  • [42]

    G. M. Sheldrick, Acta Crystallogr. 2015, C71, 3.

Purchase article
Get instant unlimited access to the article.
$42.00
Log in
Already have access? Please log in.


or
Log in with your institution

Journal + Issues

Zeitschrift für Naturforschung B is an international scientific journal which publishes original papers, microreviews, and letters from all areas of inorganic chemistry, solid state chemistry, coordination chemistry, molecular chemistry, and organic chemistry.

Search