Reactions of Arylvinylidenecyclopropanes with Bromine and Iodine

Abstract

Reactions of arylvinylidenecyclopropanes 1 with equimolar amount of bromine or iodine at low temperature produced the corresponding addition products 2, 3 and 5, 6 in moderate to good yields at -40 °C and -100 °C, respectively. On the other hand, the reactions of 1 with equimolar amount of iodine gave the corresponding iodinated naphthalene derivatives 4 via the ­corresponding addition products 3 under similar conditions at 25 °C. The further transformation of the addition product 6a has been presented.

Key words

arylvinylidenecyclopropanes - bromine - iodine - addition reaction - iodinated naphthalene derivatives

References and Notes

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6

The crystal data of 2c has been deposited in CCDC with number 273885. Empirical formula: C₂₄H₂₀Br₂; formula weight: 468.22; crystal color, habit: colorless, prismatic; crystal dimensions: 0.506 × 0.367 × 0.331 mm; crystal system: triclinic; lattice type: primitive; lattice parameters: a = 8.721 (3)Å, b = 11.157 (3)Å, c = 11.857 (3)Å, α = 109.253 (5)°, β = 106.367 (5)°, γ = 95.731 (5)°, V = 1021.1 (5)ų; space group: P-1; Z = 2; D _calcd = 1.523 g/cm³; F ₀₀₀ = 468; diffractometer: Rigaku AFC7R; residuals: R1 = 0.0739, wR2 = 0.1669. A colorless solid, mp 175.1-176.3 °C. IR (CH₂Cl₂): 3052, 3018, 2960, 2920, 2851, 1613, 1591, 1513, 1488, 1442, 1381, 1261, 1030, 813, 699, 745 cm^-1. ¹H NMR (300 MHz, CDCl₃, TMS): δ = 1.22 (1 H, dd, J ₁ = 8.1 Hz, J ₂ = 8.1 Hz, CH), 1.70 (1 H, dd, J ₁ = 8.7 Hz, J ₂ = 8.7 Hz, CH), 2.40 (3 H, s, Me), 2.90 (1 H, dd, J ₁ = 8.1 Hz, J ₂ = 8.1 Hz, CH), 6.94-7.08 (4 H, m, Ar), 7.16-7.26 (5 H, m, Ar), 7.33-7.43 (5 H, m, Ar). MS (EI): m/z (%) = 468 (1.75) [M⁺], 389 (13.50), 388 (21.71), 387 (14.75), 309 (15.26), 308 (67.40), 307 (100), 293 (26.93), 292 (32.96), 229 (55.53), 215 (85.84), 189 (18.23), 105 (13.53). HRMS (EI): m/z calcd for C₂₄H₂₀Br₂ [M⁺]: 465.9916; found: 465.9932.

7

The spectroscopic data (¹H NMR and ¹³C NMR spectral data) and analytic data of the compounds shown in Tables [1 ] - [4] , Scheme [1] and the detailed description of experimental procedures are available free of charge via the Internet.

11

General Reaction Procedure.
A solution of iodine (88 mg, 0.3 mmol) in DCE (5.0 mL) was added dropwise into a solution of diphenylvinylidene-cyclopropane (1a, 76 mg, 0.3 mmol) in DCE (2.0 mL). The reaction mixture was stirred for 6 h at -40 °C (monitored by TLC). After the starting materials 1a were consumed. The solvent in filtration was removed under reduced pressure and the residue was subjected to a flash column chromatography to give the desired product 3a (133 mg, 81%) as a yellow solid.