ORDER
REPRINTS
HALOGENATION OF AROMATICS
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4-Bromo-6-chloro-resorcinol 8. Method B was used for the preparation
of 3a, then 1 eq. of NaCl and an other amount of DMD were added to the
mixture. After additions were completed, the usual work up gave 8 which
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resulted pure from NMR analysis. H-NMR, d (ppm): 3.90 (s, 3H), 3.91 (s,
3H), 6.50 (s, 1H), 7.49 (s, 1H). 13C-NMR, d (ppm): 56.3, 56.5, 97.5, 101.8,
114.4, 113.1, 135.8, 155.1. Analysis: calc. for C6H4BrClO2 C 32.25, H 1.80;
found C 32.3, H 2.0.
5,7,40-Trimethoxy-6,8-dichloro-flavanone 10. Method A, quant. yield.
1H-NMR, d (ppm): 2.88 (dd, 1H, J ¼ 3, 16.4), 3.07 (dd, 1H, J ¼ 13, 16.4),
3.81 (s, 3H), 3.89 (s, 3H), 3.96 (s, 3H), 5.48 (dd, 1H, J ¼ 3, 13), 6.93 (d, 1H,
J ¼ 5.5), 7.39 (d, 1H, 5.5). 44.8, 55.3, 60.9, 61.8, 79.3, 113.4, 114.2, 127.5,
129.7, 156.0, 157.4, 158.5, 160.0, 188.6. Analysis: calc. for C18H16Cl2O5 C
56.41, H 4.21; found C 56.2, H 4.5.
5,7-Dihydroxy-6,8-dichloro-flavone 12a. Method A, yield 72%.
1H-NMR (DMSO-d6), d (ppm): 7.16 (s, 1H), 7.52–7.68 (m, 3H), 8.08–8.18
(m, 2H). 99.4, 103.9, 104.5, 105.3, 126.4, 129.3, 130.2, 132.5, 155.1, 155.9,
161.6, 163.5, 170.9, 181.7. Analysis: calc. for C15H8Cl2O4 C 55.76, H 2.5;
found C 55.9, H 2.8.
5,7-Dimethoxy-6,8-dichloro-flavone 12b. Method A, yield 87%.
1H-NMR, d (ppm): 3.99 (s, 3H), 4.04 (s, 3H), 6.77 (s, 1H), 7.48–7.60 (m,
3H), 7.90–8.20 (m, 2H). 13C-NMR, d (ppm): 61.2, 62.1, 108.3, 14.2, 16.5,
121.5, 126.1, 129.1, 130.6, 131.9, 152.2, 154.8, 156.9, 161.5, 175.9. Analysis:
calc. for C17H12Cl2O4 C 58.14, H 3.44; found C 57.8, H 3.4.
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4-Chloro-anisole 14a. Method B, yield 82%. H-NMR, d (ppm): 3.81
(s, 3H), 6.84 (bd, 2H, J ¼ 9.5), 7.26 (bd, 2H, J ¼ 9.5). 13C-NMR, d (ppm):
55.4, 115.1, 127.7, 129.3, 158.2.
4-Bromo-anisole 14b. Method B, yield 96%. By NMR analysis of the
crude, 1.3% of 2-bromo-anisole was also detected. An excess of DMD did
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not give the dibromo derivative in any condition. H-NMR, d (ppm): 3.80
(s, 3H), 6.78 (bd, 2H, J ¼ 9.2), 7.38 (bd, 2H, J ¼ 9.2). 13C-NMR, d (ppm):
55.4, 112.8, 115.7, 132.2, 158.7.
4-Iodo-anisole 14c. Method B, yield 30%. Further additions of DMD
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resulted in decomposition of the mixture. H-NMR, d (ppm): 3.79 (s, 3H),
6.78 (bd, 2H, J ¼ 9.4), 7.55 (bd, 2H, J ¼ 9.4). 13C-NMR, d (ppm): 55.3, 82.7,
116.4, 138.2, 159.5.
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2-Chloro-anisole 15a. Method B, yield 13%. H-NMR, d (ppm): 3.89
(s, 3H), 6.89 (m, 2H), 7.21 (m, 1H), 7.4 (dd, 1H, J ¼ 2.2, 8.1).
1H-NMR, d (ppm): 13C-NMR, d (ppm): 56.0, 112.1, 121.2, 125.5, 127.5,
130.2, 155.0.
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2,4-Dichloro-anisole 16a. Method B, yield 96%. H-NMR, d (ppm):
3.9 (s, 3H), 6.86 (d, 1H, J ¼ 8.8), 7.22 (dd, 1H, J ¼ 2.2, 8.8), 7.38 (d, 1H,
J ¼ 2.2). 13C-NMR, d (ppm): 56.3, 112.8, 123.3, 125.6, 127.6, 129.9, 153.9.