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Zeitschrift für Naturforschung B

A Journal of Chemical Sciences

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

Orthoamides and Iminium Salts XCII. Synthesis and reactions of orthoamides derived from ethynylated terpene derivativesa

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, Fax: +49-7361-5762250
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Jochen Mezger
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Ralf Kreß
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
  • Other articles by this author:
  • De Gruyter OnlineGoogle Scholar
/ Wolfgang Frey
  • Institut für Organische Chemie, Universität Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany
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Published Online: 2018-06-13 | DOI: https://doi.org/10.1515/znb-2018-0011

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.

Keywords: camphor; CH2- and NH2-acidic compounds; condensation reaction; ethynylation; β-ionone; orthoamide derivatives

Dedicated to: Professor Horst Hartmann on the occasion of his 80th birthday.

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About the article

aOrthoamide und Iminiumsalze XCI: siehe Lit. [1]


Received: 2018-01-11

Accepted: 2018-02-19

Published Online: 2018-06-13


Citation Information: Zeitschrift für Naturforschung B, 20180011, ISSN (Online) 1865-7117, ISSN (Print) 0932-0776, DOI: https://doi.org/10.1515/znb-2018-0011.

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