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Synthesis 2009(15): 2547-2552  
DOI: 10.1055/s-0029-1217404
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of 11,12-Didehydrodibenzo[a,e]cycloocten-5(6H)-one: A Strained Eight-Membered Alkyne

Stefan C. Kornmayer, Frank Rominger, Rolf Gleiter*
Organisch-Chemisches Institut der Universität Heidelberg, Im Neuenheimer Feld 270, 69120 Heidelberg, Germany
Fax: +49(06221)544205; e-Mail: rolf.gleiter@oci.uni-heidelberg.de ;
Further Information

Publication History

Received 25 February 2009
Publication Date:
23 June 2009 (online)

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Abstract

An eight-step synthesis of 11,12-didehydrodibenzo[a,e]cycloocten-5(6H)-one (10) was developed. The structure of 10 was assigned by spectroscopic means and confirmed by X-ray analysis of its 2,4-dinitrophenylhydrazone derivative. Reaction of the triple bond of 10 with dicarbonyl(η5-cyclopentadienyl)cobalt or dicarbonyl(η5-pentamethylcyclopentadienyl)cobalt gave the corresponding metal-stabilized cyclobutadiene complexes.

Key words

alkynes - cycloadditions - eliminations - oxidations - ring expansion.

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8

X-ray structure analysis of diphenylhydrazone of 10: red crystals (plates), dimensions 0.20 × 0.13 × 0.08 mm³, crystal system monoclinic, space group P21/n, Z = 4, a = 12.0543(13) Å, b = 8.2733(9) Å, c = 19.102(2) Å, α = 90˚, β = 105.447(5)˚, γ = 90˚, V = 1836.2(4) ų, ρ = 1.441 g cm-³, T = 200(2) K, radiation MoKα, λ = 0.71073 Å, 0.3˚ ω-scans with CCD area detector, covering a whole sphere in reciprocal space; 9253 reflections measured, 1725 unique [R(int) = 0.0473], 1322 observed [I > 2σ(I)]; µ = 0.102 mm-¹, T min = 0.99, T max = 0.98; 275 parameters refined, hydrogen atoms were treated using appropriate riding models, goodness of fit 1.17 for observed reflections, final residual values R1 (F) = 0.059, wR(F ²) = 0.139 for observed reflections, residual electron density -0.21 to 0.19 eÅ-³.

11

X-ray structure analysis of 20: red crystals (plates), dimensions 0.57 × 0.09 × 0.08 mm³, crystal system triclinic, space group P1, Z = 4, a = 8.7426(7) Å, b = 17.2931(16) Å, c = 19.5099(16) Å, α = 106.941(3)˚, β = 92.274(2)˚, γ = 104.589(2)˚, V = 2710.2(4) ų, ρ = 1.426 g cm-³, T = 200(2) K, radiation MoKα, l = 0.71073 Å, 0.3˚ ω-scans with CCD area detector, covering a whole sphere in reciprocal space; 28788 reflections measured, 13417 unique [R(int) = 0.0616], 9808 observed [I >2σ(I)]; µ = 0.717 mm-¹, T min = 0.69, T max = 0.94; 798 parameters refined, hydrogen atoms were treated using appropriate riding models, goodness of fit 1.23 for observed reflections, final residual values R1 (F) = 0.106, wR(F ²) = 0.187 for observed reflections, residual electron density -0.67 to 1.04 eÅ-³.

12

X-ray structure analysis of 21: red crystals (plates), dimensions 0.15 × 0.07 × 0.05 mm³, crystal system monoclinic, space group P21/c, Z = 4, a = 11.753(2) Å, b = 12.508(3) Å, c = 20.743(4) Å, α = 90˚, β = 91.326(6)˚, γ = 90˚, V = 3048.4(11) ų, ρ = 1.374 g cm-³, T = 200(2) K, radiation MoKα, l = 0.71073 Å, 0.3˚ ω-scans with CCD area detector, covering a whole sphere in reciprocal space; 12809 reflections measured, 2422 unique [R(int) = 0.1342], 1936 observed [I >2σ(I)]; µ = 1.374 mm-¹, T min = 0.92, T max = 0.97; 216 parameters refined, hydrogen atoms were treated using appropriate riding models, goodness of fit 1.18 for observed reflections, final residual values R1 (F) = 0.127, wR(F ²) = 0.213 for observed reflections, residual electron density -0.39 to 0.55 eÅ-³.