One-Pot Synthesis of 2H-Chromene Derivatives from ortho-Naphthoquinones

Abstract

A general one-pot synthesis for 2H-chromenes is reported from ortho-naphthoquinones and allyltriphenylphosphonium salts, [(RMeC=CHCH₂)Ph₃P]⁺Br^-, in the presence of aqueous NaOH and chloroform at room temperature.

chromenes - Wittig reaction - one-pot cyclisation - naphthoquinones

References and Notes

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Data was obtained at 120 K with Mo KGk-α radiation by means of the Enraf Nonius KappaCCD area detector diffractometer of the EPSRC crystallographic service, based at the University of Southampton. Data collection was carried out under the control of the program COLLECT^17a and data reduction and unit cell refinement were achieved with the COLLECT^17a and DENZO programs.^17b Correction for absorption, by comparison of the intensities of equivalent reflections, was applied using the program SADABS.^17c The program ORTEP-3 for Windows^17d was used in the preparation of Figure [3] and SHELXL-97^17e and PLATON^17f in the calculation of molecular geometry. The structure was solved by direct methods using SHELXS-97^17g and fully refined by means of the program SHELXL-97.^17e In the final stages of refinement, hydrogen atoms were introduced in calculated positions and refined with a riding model.

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Crystal data collected at 120 K, colourless crystal: 0.16 × 0.10 × 0.06 mm³. Formula: C₂₀H₂₂O₂; M = 294.38; monoclinic, P21/c, a = 8.657(2) Å, b = 7.9525(17) Å, c = 23.385(6) Å, β = 92.815(9)°, Z = 4, V = 1608.0(7) ų, 3696 independent reflections [R(int) = 0.1482], 1562 observed reflections [I >2s(I)]; parameters refined: 203; number of restraints: 0; R(F): 0.1839 (obs. data), Δρ_max = 0.28 Å^-3. CCDC deposition no: 292382.

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<A NAME="RS04407ST-22">22</A>

General Procedure for 2 H -Chromenes 7-10: A mixture of the naphthoquinone (0.02 mol), allyltriphenylphosphonium salt (0.04 mol), CHCl₃ (15 mL) and aq 50% NaOH (15 mL, 0.19 mol) was vigorously stirred for 48 h at r.t. The organic phase was collected, washed with H₂O (3 × 10 mL), dried over MgSO₄ and the solvent was evaporated. Purification of the crude product was achieved by flash column chromatography using hexane-CH₂Cl₂ as eluent.
6-Methoxy-3,3-dimethyl-3 H -benzo[ f ]chromene (7a): IR (KBr): 2971, 2938, 1634, 1588, 1574, 1515, 1464, 1450, 1443, 1411, 1379, 1351, 1283, 1247, 1220, 1207, 1199, 1160, 1130, 1119, 1092, 996, 981, 885, 841, 755, 727, 694, 626 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.50 (s, 6 H, Me), 3.98 (s, 3 H, OMe), 5.58 (d, J = 9.8 Hz, 1 H, H-2), 6.48 (s, 1 H, H-5), 6.95 (d, J = 9.8 Hz, 1 H, H-1), 7.30 (ddd, J = 1.2, 6.8, 8.5 Hz, 1 H, H-8), 7.49 (ddd, J = 1.2, 6.8, 8.3 Hz, 1 H, H-9), 7.89 (ddd, J = 0.7, 1.2, 8.3 Hz, 1 H, H-7), 8.17 (ddd, J = 0.7, 1.2, 8.5 Hz, 1 H, H-10). ¹³C NMR (75.0 MHz, CDCl₃): δ = 27.4 (Me), 27.4 (Me), 55.5 (OMe), 76.2 (C-3), 97.4 (C-5), 106.8 (C-10b), 118.1 (C-1), 120.9 (C-10), 121.3 (C-6a), 122.3 (C-7), 122.5 (C-8), 126.0 (C-2), 127.1 (C-9), 130.4 (C-10a), 151.6 (C-4a), 156.4 (C-6). EIMS: m/z (%) = 240 (22) [M⁺], 225 (100), 210 (15). HRMS: m/z calcd for C₁₆H₁₆O₂: 240.1150; found: 240.1139.
2,2,6,6-Tetramethyl-3,4-dihydro-2 H ,6 H -1,5-dioxatri­-phenylene (8a): mp 89-90 °C. IR (KBr): 2975, 2934, 1637, 1578, 1510, 1465, 1453, 1428, 1418, 1396, 1383, 1369, 1360, 1325, 1289, 1253, 1237, 1220, 1195, 1159, 1137, 1119, 1003, 974, 881, 762, 732, 710, 691, 665, 646 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.41 (s, 6 H, Me), 1.47 (s, 6 H, Me), 1.86 (t, J = 6.8 Hz, 2 H, H-3), 2.77 (t, J = 6.8 Hz, 2 H, H-4), 5.54 (d, J = 10.0 Hz, 1 H, H-7), 6.95 (d, J = 10.0 Hz, 1 H, H-8), 7.27 (ddd, J = 1.2, 6.8, 8.3 Hz, 1 H, H-11), 7.41 (ddd, J = 1.2, 6.8, 8.3 Hz, 1 H, H-10), 7.85 (ddd, J = 0.5, 1.2, 8.3 Hz, 1 H, H-12), 8.14 (ddd, J = 0.5, 1.2, 8.3 Hz, 1 H, H-9). ¹³C NMR (75 MHz, CDCl₃): δ = 19.9 (C-4), 29.3 (Me), 29.3 (Me), 78.6 (C-6), 34.7 (C-3), 77.1 (C-2), 78.6 (C-6), 106.6 (C-8a), 110.3 (C-4a), 121.2 (C-9), 123.3 (C-12), 123.6 (C-12a), 124.6 (C-11), 124.8 (C-8), 128.0 (C-7), 128.7 (C-10), 131.6 (C-8b), 152.5 (C-4b), 152.6 (C-13). EIMS: m/z (%) = 294 (44) [M⁺], 279 (77), 223 (100). HRMS: m/z calcd for C₂₀H₂₂O₂: 294.1620; found: 294.1617.
5,6,7,8-Tetrachloro-2,2-dimethyl-2 H -chromene (10): yellow solid; mp 83-84 °C. IR (KBr): 2924, 2870, 2854, 1681, 1600, 1455, 1428, 1392, 1379, 1327, 1308, 1237, 1225, 1205, 1151, 1051, 1018, 996, 970, 924, 900, 834, 791, 663 cm^-1. ¹H NMR (300 MHz, CDCl₃): δ = 1.87 (d, J = 1.5 Hz, 3 H, Me), 1.88 (d, J = 1.5 Hz, 3 H, Me), 5.55 (dsept, J = 1.5, 8.3 Hz, 1 H, H-2), 6.92 (d, J = 8.3 Hz, 1 H, H-1). ¹³C NMR (75 MHz, CDCl₃): δ = 19.0 (Me), 26.4 (Me), 30.0 (C-3), 111.0 (C-1), 112.9 (C-5), 118.3 (C-2), 125.1 (C-8a), 126.0 (C-7), 128.0 (C-6), 144.9 (C-8), 146.7 (C-4a).