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Helvetica Chimica Acta – Vol. 94 (2011)
3-[2-Bromo-5-(methoxymethoxy)phenyl]-3-oxo-2-phenylpropanal (1k). Yellow oil. IR: 3081, 3056,
3024, 2908, 2853, 2769, 1663, 1575, 1239, 1089, 756, 710. 1H-NMR (400 MHz, CDCl3): 9.52 (s, 1 H); 7.59
(d, J ¼ 8.9, 1 H); 7.50 – 7.41 (m, 3 H); 7.36 – 7.32 (m, 2 H); 7.21 (d, J ¼ 2.9, 1 H); 7.06 (dd, J ¼ 8.9, 2.9,
1 H); 5.24 (s, 2 H); 3.50 (s, 3 H). 13C-NMR (101 MHz, CDCl3): 189.0; 157.0; 152.6; 141.8; 137.6; 134.4;
132.6; 129.9; 128.9; 128.5; 119.9; 118.8; 114.8; 94.9; 56.6. HR-ESI-MS: 382.9902 ([M þ Na ꢀ 2]þ,
C17H13BrNaOþ4 ; calc. 382.9895).
3-(2-Bromophenyl)-2-(naphthalen-2-yl)-3-oxopropanal (1l). White solid. M.p. 116 – 1188. IR: 3083,
3055, 2958, 2920, 2849, 2757, 1679, 1577, 1220, 1072, 758, 719. 1H-NMR (400 MHz, CDCl3): 9.56 (s, 1 H);
7.93 (d, J ¼ 8.5, 1 H); 7.91 – 7.87 (m, 2 H); 7.85 (s, 1 H); 7.75 (d, J ¼ 8.1, 1 H); 7.57 (d, J ¼ 7.7, 1 H); 7.53 –
7.51 (m, 2 H); 7.48 – 7.43 (m, 2 H); 7.41 – 7.35 (m, 1 H). 13C-NMR (75 MHz, CDCl3): 189.0; 153.2; 141.9;
136.9; 133.7; 133.4; 133.3; 131.8; 131.3; 130.0; 129.6; 128.5; 128.1; 128.0; 127.2; 126.9; 126.5; 123.3. HR-
ESI-MS: 372.9823 ([M þ Na ꢀ 2]þ, C19H13BrNaO4þ ; calc. 372.9840).
3-(2-Bromophenyl)-2-methyl-3-oxopropanal (1m). White solid. M.p. 162 – 1638. IR: 3071, 2924, 2598,
1647, 1562, 1346, 1233, 775. 1H-NMR (400 MHz, CDCl3): 14.62 (d, J ¼ 6.0, 1 H); 8.35 (d, J ¼ 5.4, 1 H); 7.62
(d, J ¼ 7.9, 1 H); 7.39 (d, J ¼ 7.5, 1 H); 7.33 – 7.22 (m, 2 H); 1.68 (s, 3 H). 1H-NMR (400 MHz,
(D6)DMSO): 11.17 (s, 1 H); 7.65 (d, J ¼ 7.9, 1 H); 7.42 (t, J ¼ 7.3, 1 H); 7.35 (t, J ¼ 6.9, 1 H); 7.29 (d, J ¼
6.9, 1 H); 7.04 (s, 1 H); 1.73 (s, 3 H). 13C-NMR (101 MHz, (D6)DMSO): 194.8; 184.2; 162.3; 132.6; 130.6;
128.8; 127.5; 118.9; 115.0; 7.5. HR-ESI-MS: 240.9868 (Mþ, C10H10BrO2þ ; calc. 240.9864).
General Procedure for the Synthesis of 2. A mixture of 1 (0.5 mmol), CuI (10 mg, 0.05 mmol),
K2CO3 (138 mg, 1 mmol), 2-picolinic acid (12 mg, 0.01 mmol), and dry DMF (3 ml) in a flask filled with
N2 was stirred at 135 – 1408 for 20 h. The mixture was separated between AcOEt (3 ꢁ 20 ml) and H2O
(30 ml). The org. layer was dried (Na2SO4), filtered, evaporated under vacuum, and purified by FC
(hexane/AcOEt) to give product 2. For anal. data of compounds 2a, 2b, 2g, and 2h, see [9]. For
compounds 2e, 2i, 2l, and 2m, see [18 – 21], resp.
7-Phenyl-8H-[1,3]dioxolo[4,5-g]chromen-8-one (2c). White solid (85 mg, 64%). M.p. 152 – 1538. IR:
3091, 3040, 2901, 2780, 1636, 1611, 1260, 1037, 746, 703. 1H-NMR (400 MHz, CDCl3): 7.93 (s, 1 H); 7.73 –
7.49 (m, 3 H); 7.42 – 7.37 (m, 3 H); 6.85 (s, 1 H); 6.09 (s, 2 H). 13C-NMR (101 MHz, CDCl3): 176.4; 154.7;
153.9; 153.6; 147.5; 133.1; 130.2; 129.7; 129.4; 125.9; 120.8; 104.0; 103.7; 99.1. HR-MS: 266.0580 (Mþ,
C16H10Oþ4 ; calc. 266.0579).
8-Methyl-3-phenyl-4H-1-benzopyran-4-one (2d). White solid (84 mg, 71%). M.p. 111 – 1128. IR:
3071, 3032, 2925, 2851, 2780, 1654, 1584, 1273, 1056, 770, 705. 1H-NMR (400 MHz, CDCl3): 8.17 (d, J ¼
8.0, 1 H); 8.08 (s, 1 H); 7.62 – 7.55 (m, 2 H); 7.52 (d, J ¼ 7.2, 1 H); 7.46 (t, J ¼ 7.4, 2 H); 7.42 – 7.37 (m, 1 H);
7.32 (t, J ¼ 7.6, 1 H); 2.51 (s, 3 H). 13C-NMR (75 MHz, CDCl3): 176.6; 154.8; 153.0; 134.6; 132.1; 129.0;
128.6; 128.2; 127.6; 125.1; 124.9; 124.5; 124.0; 15.7. HR-MS: 236.0836 (Mþ, C16H12O2þ ; calc. 236.0837).
3-(2-Chlorophenyl)-4H-1-benzopyran-4-one (2f). White solid (57 mg, 34%). M.p. 129 – 1308. IR:
3085, 3061, 3041, 3014, 2921, 2852, 1634, 1469, 1234, 1078, 746, 711. 1H-NMR (400 MHz, CDCl3): 8.32 (d,
J ¼ 7.5, 1 H); 7.98 (s, 1 H); 7.71 (d, J ¼ 7.2, 1 H); 7.54 – 7.49 (m, 2 H); 7.45 (t, J ¼ 7.7, 1 H); 7.39 – 7.32 (m,
3 H). 13C-NMR (75 MHz, CDCl3): 175.8; 163.1; 156.6; 154.6; 134.8; 134.0; 132.4; 131.1; 130.1; 127.3;
127.0; 126.7; 125.6; 124.4; 118.4. HR-MS: 256.0294 (Mþ, C15H9ClO2þ ; calc. 256.0291).
3-(3,5-Dimethylphenyl)-4H-1-benzopyran-4-one (2j). White solid (70 mg, 56%). M.p. 86 – 878. IR:
1
3072, 2918, 2852, 2731, 1651, 1467, 1307, 1188, 764, 692. H-NMR (400 MHz, CDCl3): 8.32 (d, J ¼ 7.9,
1 H); 8.00 (s, 1 H); 7.68 (t, J ¼ 7.7, 1 H); 7.51 – 7.37 (m, 2 H); 7.18 (s, 2 H); 7.03 (s, 1 H); 2.37 (s, 6 H).
13C-NMR (101 MHz, CDCl3): 176.6; 156.4; 153.2; 138.3; 133.8; 131.9; 130.2; 127.0; 126.7; 125.9; 125.4;
124.8; 118.3; 21.6. HR-MS: 250.0994 (Mþ, C17H14O2þ ; calc. 250.0994).
6-(Methoxymethoxy)-3-phenyl-4H-chromen-4-one (2k). White solid (90 mg, 64%). M.p. 113 – 1148.
IR: 3067, 3040, 2958, 2902, 2861, 2825, 1648, 1489, 1279, 1068, 750, 699. 1H-NMR (400 MHz, CDCl3): 8.03
(s, 1 H); 7.91 (d, J ¼ 2.8, 1 H); 7.59 (d, J ¼ 7.4, 2 H); 7.50 – 7.43 (m, 3 H); 7.43 – 7.37 (m, 2 H); 5.29 (s, 2 H);
3.53 (s, 3 H). 13C-NMR (101 MHz, CDCl3): 175.9; 169.9; 154.4; 153.0; 151.5; 131.9; 128.9; 128.5; 128.1;
124.6; 124.1; 119.4; 110.2; 94.8; 56.2. HR-MS: 282.0893 (Mþ, C17H14O4þ ; calc. 282.0892).