Synthesis of 3-Alkylseleno-2-cylcobutenone via [2+2] Cycloaddition Reaction of Alkyneselenolate with Diphenylketene

 

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Abstract

3-Alkylseleno-2-cyclobutenones were synthesized by reaction of alkyneselenolate with diphenylketene via [2+2] cycloaddition. The complete structure of the 2-cyclobutenone was determined by X-ray diffraction.

References

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This work was first reported at the 222nd National Meeting of the American Chemical Society, Chicago, August 26-30, 2001.

Procedure: 3-Methylseleno-2,4,4-triphenyl-2-cyclo-butenone 5a: Lithium alkyneselenolate 3 (2 equiv), generated in situ from phenylacetylene (2 equiv), n-BuLi
(2 equiv) and elementary selenium (2 equiv.), was added to THF solution of diphenylketene 2 which was generated from diphenylacetyl chloride 1 (1 equiv) and triethylamine (1 equiv) under argon atmosphere. Moreover, methyl iodide 4a (2 equiv) was added to the mixture and was stirred at room temperature for 1 h. The mixture was extracted with diethyl ether and washed with saturated NaCl solution. The organic layer was dried over sodium sulfate and evaporated to dryness. The residue was purified by flash chromatography on silica gel with n-hexane-diethyl ether (50:1) to give 0.20 g of 5a (51%) as pale yellow crystals; mp 120.9-122.3 °C; IR (KBr) 1734 cm^-1; ¹H NMR (CDCl₃) δ 2.12 (s, 3 H, CH₃), 7.27-7.47 (m, 13 H, Ar), 7.79 (d, J = 7.6 Hz, 2 H, Ar); ¹³C NMR (CDCl₃) δ 7.9, 81.7, 127.1, 127.5, 128.2, 128.5, 128.6, 128.8, 129.8, 138.7, 145.7, 169.2, 185.3; ⁷⁷Se NMR (CDCl₃) δ 257.8; MS (CI): m/z = 391 [M⁺ + 1]; Anal. Calcd for C₂₃H₁₈OSe: C, 70.95; H, 4.66. Found: C, 70.63; H, 4.66%. 3-Ethylseleno-2,4,4-triphenyl-2-cyclobutenone 5b: Pale yellow crystals; mp 111.4-113.2 °C; IR (KBr) 1741cm^-1; ¹H NMR (CDCl₃) δ 1.04 (t, J = 7.6 Hz, 3 H, CH₃), 2.86 (q, J = 7.6 Hz, 2 H, CH₂), 7.27-7.48 (m, 13 H, Ar), 7.80 (d, J = 7.6 Hz, 2 H, Ar); ¹³C NMR (CDCl₃) δ 14.7, 22.4, 81.6, 127.2, 127.5, 128.3, 128.5, 128.6, 129.9, 138.8, 145.2, 169.7, 185.4; ⁷⁷Se NMR (CDCl₃) δ 349.2; MS (CI): m/z = 405 [M⁺ + 1]; Anal. Calcd for C₂₄H₂₀OSe: C, 71.46; H, 5.00. found: C, 71.10; H, 5.01%.

Crystallographic data for the structural analysis have been deposited with the Cambridge Crystallographic Data Centre as supplementary publication, CCDC No. 176955 for 5b. Copies of this information can be obtained, free of charge, on application to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK (fax:+44(1233)336033 or e-mail: deposit@ccdc.cam.ac.uk).