Efficient Higher-Order Cycloaddition Reactions of 8,8-Dicyanoheptafulvene with Dienes

Vijay Nair; K. Gopalakrishnan Abhilash; Akkattu T. Biju; Eringathodi Suresh

doi:10.1055/s-2007-983711

PAPER

Efficient Higher-Order Cycloaddition Reactions of 8,8-Dicyanoheptafulvene with Dienes

Vijay Nair*^a,b, K. Gopalakrishnan Abhilash^a, Akkattu T. Biju^a, Eringathodi Suresh^c
^a Organic Chemistry Section, Regional Research Laboratory (CSIR), Trivandrum 695019, India
Fax: +91(471)2491712; e-Mail: vijaynair_2001@yahoo.com;
^b Jawaharlal Nehru Centre for Advanced Scientific Research, Bangalore 560064, India
^c Central Salt and Marine Chemicals Research Institute (CSIR), Bhavnagar 364002, India

Abstract

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Abstract

The cycloaddition reactions of 8,8-dicyanoheptafulvene with electron-rich dienes afforded the higher order cycloaddition products in excellent yields. With cyclic dienes as well as dimethoxybutadiene the [8+2] adducts were obtained exclusively. With methyl- and dimethylbutadienes the [6+4] adducts were the only products isolated.

Key words

cycloadditions - bicyclic compounds - polycycles - dicyanoheptafulvene - tetrahydroazulenes

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References

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Crystal data for 3a: empirical formula C₃₂H₃₂N₄, formula weight 472.62, triclinic, space group P-1, a = 7.123(2) Å, b = 8.306(3) Å, c = 11.506(4) Å, α = 87.363(6)°, β = 81.053(7)°, γ = 83.939(6)°, V = 668.4(4) Å³, Z = 1, D _calcd = 1.174 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.070 mm^-1, F(000) = 252, T = 293(2) K, crystal size = 0.22 × 0.10 × 0.06 mm. CCDC 639690 contains the supplementary crystallographic data for this compound.

Crystal data for 3c: empirical formula C₁₇H₁₆N₂O, formula weight 264.32, monoclinic, space group P2₁/n, a = 8.4450(12) Å, b = 13.0730(18) Å, c = 12.8118(18) Å, α = 90°, β = 99.069(3)°, γ = 90°, V = 1394.6(3) Å³, Z = 4, D _calcd = 1.259 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.080 mm^-1, F(000) = 560, T = 273(2) K, crystal size = 0.30 × 0.20 × 0.12 mm. CCDC 639691 contains the supplementary crystallographic data for this compound.

Crystal data for 3e: empirical formula C₁₆H₁₆N₂O₂, formula weight 268.31, monoclinic, space group = P2₁/n, a = 8.0664(8) Å, b = 14.2902(15) Å, c = 13.3056(14) Å, α = 90°, β = 103.564(2)°, γ = 90°, V = 1491.0(3) Å³, Z = 4, D _calcd = 1.195 Mg/m³, λ = 0.71073 Å, absorption coefficient = 0.080 mm^-1, F(000) = 568, T = 296(2) K, crystal size = 0.34 × 0.28 × 0.22 mm. CCDC 639692 contains the supplementary crystallographic data for this compound.

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