Monatshefte für Chemie / Chemical Monthly

, Volume 119, Issue 5, pp 583–589 | Cite as

Activation of alkynes by the dinitrogen complex [CoH(N2)(PPh3)3] towards catalytic oligomerization and cyclization reactions

  • Rudolf Herrmann
  • Armando J. L. Pombeiro
Organische Chemie Und Biochemie

Abstract

The complex [CoH(N2)(PPh3)3] catalyses oligomerization and cyclization reactions of alkynes under mild conditions. Hence, alkyne cocyclotrimerization to benzene derivatives was mainly observed for ethyl propiolate, affording the three possible isomers of tricarbethoxybenzene; phenylacetylene undergoes mainly linear dimerization totrans-PhC≡CCH=CHPh and trimerization; linear dimers are also the predominant products from 3-hexyne, but 1-octyne (with a long chain) undergoes mainly isomerization to 2-octyne; higher oligomers are also usually formed. Except for ethyl propiolate, hydrogenated dimers are detected in low yields (e.g.trans,trans-PhCH=CHCH=CHPh from phenylacetylene), whereas 3-hexene is formed in considerable yield from 3-hexyne. A novel type of cocyclization reaction with a nitrile (NCMe) appears to occur with phenylacetylene to give (although in low yield) 4,6-dimethyl-5-phenyl-pyrimidine. Alkynols are unreactive under the chosen conditions.

Keywords

Alkynes Catalysis Dinitrogen complex Nitriles Pyrimidine 

Die Aktivierung von Alkinen mit dem Distickstoffkomplex [CoH(N2)(PPh3)3] gegenüber katalytischer Oligomerisierung und Cyclisierungsreaktionen

Zusammenfassung

Der Komplex [CoH(N2)(PPh3)3] katalysiert Oligomerisations- und Cyclisierungsreaktionen von Alkinen unter milden Bedingungen. Die Cyclotrimerisierung von Propinsäureethylester ergibt die drei möglichen Isomeren von Tricarbethoxybenzol; Phenylacetylen reagiert hauptsächlich zu linearen Dimeren (vor allemtrans-PhC≡CCH=CHPh) und Trimeren; lineare Dimere herrschen auch bei 3-Hexin vor, während 1-Octin (mit langer Alkylkette) vorwiegend zu 2-Octin isomerisiert wird. In allen Fällen werden ebenfalls höhere Oligomere gebildet. Außer bei Propinsäureethylester entstehen ebenfalls in geringer Menge hydrierte Dimere (z. B.trans,trans-PhCH=CHCH=CHPh aus Phenylacetylen). Eine neue Art von Cocyclisierungsreaktion mit einem Nitril (NCMe) scheint bei der Bildung (in geringer Ausbeute) von 4,6-Dimethyl-5-phenyl-pyrimidin aus Phenylacetylen vorzuliegen. Alkinole reagieren unter den Versuchsbedingungen nicht.

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Copyright information

© Springer-Verlag 1988

Authors and Affiliations

  • Rudolf Herrmann
    • 1
  • Armando J. L. Pombeiro
    • 2
  1. 1.Organisch-Chemisches Institut der Technischen Universität MünchenGarchingFederal Republic of Germany
  2. 2.Centro de Química Estrutural, Complexo IInstituto Superior TécnicoLisboa CodexPortugal

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