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DOI: 10.1055/s-2002-25355
The First Facile Synthesis of Some 1,2a,3,8b-Tetrahydro-2H-Cyclobuta[c] Chromenes Through Intramolecular Alkylation of an Aromatic Ring by a Cyclobutanone
Publication History
Publication Date:
07 February 2007 (online)
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Abstract
Starting from cyclobutanones several new chromenes containing a cyclobutane ring are prepared. Ring fission of these derivatives gives easy access to functionalized 3-isoflavenes.
Key words
cyclopropanes - cyclobutanones - electrophilic aromatic substitutions - ring opening - kinetic resolution
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References
It has not been possible to isolate the oxaspiropentane 2e, as it is transformed to the corresponding cyclobutanone 3e during the epoxidation reaction.
8Typical procedure for the preparation of chromenes 4a-f: A stirred solution of cyclobutanone 3 (2.7 mmol) and p-toluenesulfonic acid (0.27 mmol, 0.046 g) in benzene (10 mL) was refluxed for 6 h. The reaction mixture was diluted with CH2Cl2 and washed with 10% NaHCO3 and brine, dried (Na2SO4) and evaporated to remove the solvent. The residue was purified by chromatography on silica gel with Et2O-light petroleum (1:1) as eluent.
All new compounds have been fully characterized by 1H NMR (300 MHz), 13C NMR (75.4 MHz) and mass spectra (70 eV). Analytical data for some representative derivatives are reported. 1f: colorless oil; yield: 70%. 1H NMR (CDCl3) δ: 1.00-1.22 (m. 4 H), 1.52 (d, 3 H, J = 6.6 Hz), 1.84 (s, 3 H), 5.05 (q, 1 H, J = 6.6 Hz), 6.90-7.28 (m, 5 H). 13C NMR (CDCl3) δ: 1.14, 2.76, 15.10, 19.71, 78.56, 115.65, 118.76, 120.65, 124.74, 129.12, 158.16. 3e: yellow oil; yield: 85%. 1H NMR (CDCl3) δ: 2.48-2.58 (m, 1 H), 2.73-2.82 (m, 1 H), 2.98-3.10 (m, 1 H), 3.18-3.30 (m, 1 H), 3.97, 4.23 (AB q, 2 H, J = 9 Hz), 7.22-7.44 (m, 10 H). 13C NMR (CDCl3) δ: 21.09, 44.09, 72.06, 72.54, 114.58, 121.25, 126.58, 127.50, 128.69, 129.43, 137.83, 158.43, 210.17. IR (neat, cm-1) : 1782. MS m/z: 252 [M+ (0.4)], 209(5), 195(9), 159(100), 131(23), 117(60). 4e: yellow oil; yield 60%. 1H NMR (CDCl3) δ: 2.13-2.27 (m, 1 H), 2.19 (br s, 1 H), 2.26-2.33 (m, 2 H), 2.54-2.61 (m, 1 H), 4.05,4.14 (AB q, 2 H, J = 11.4 Hz), 6.85-7.65 (m, 9 H). 13C NMR (CDCl3) δ: 19.94, 36.76, 52.91, 71.74, 72.68, 117.29, 122.08, 127.22, 127.32, 127.58, 128.57, 128.79, 129.73, 138.37, 154.17. IR (neat, cm-1) : 3450. MS m/z: 252 [M+(6)], 234(5), 224(8), 121(100). 5e: red oil; yield 56%. 1H NMR (CDCl3) δ: 2.41 (s, 3 H), 2.81 (t, 2 H, J = 7.5 Hz), 3.99 (t, 2 H, J = 7.5 Hz), 4.78 (s, 2 H), 6.81-7.64 (m, 10 H). 13C NMR (CDCl3) δ: 21.55, 26.98, 68.19, 69.39, 116.19, 121.51, 122.60, 123.25, 124.00, 127.69, 127.78, 128.02, 128.77, 128.91, 129.69, 132.69, 134.34, 13.44, 144.54, 153.89. IR (neat, cm-1): 1160,1350.