3,5-diisopropyl-3',5'-dimethoxy-[1,1'-biphenyl]-4,4'-diol
ACCEPTED MANUSCRIPT
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(16).13 40.3 mg, 61% yield. H NMR (400 MHz, CDCl3) δ 7.19
2-methoxy-6-(2-methoxynaphthalen-1-yl)-4-methylphenol
(2H, s), 6.73 (2H, s), 5.49 (1H, s), 4.81 (1H, s), 3.96 (6H, s), 3.21
(2H, m), 1.34 (6H, s), 1.32 (6H, s). 13C NMR (150 MHz, CDCl3)
δ 149.4, 147.1, 134.2, 133.9, 133.8, 122.3, 104.0, 56.38, 56.37,
27.4, 22.8. HRMS (ESI+) m/z calculated for [(C20H26O4)H]+
331.1904 found 331.1901.
(10).11c 25.9 mg, 44% yield. H NMR (400 MHz, CDCl3) δ 7.92
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(1H, d, J = 8.8 Hz), 7.84 (1H, d, J = 8.0 Hz), 7.50 (1H, d, J = 8.0
Hz), 7.41 (1H, d, J = 8.8 Hz), 7.36-7.34 (2H, m), 6.80 (1H, s),
6.67 (1H, s), 5.38 (1H, s), 3.96 (3H, s), 3.90 (3H, s), 2.37 (3H,
s). 13C NMR (150 MHz, CDCl3) δ 154.3, 146.7, 141.4, 133.5,
129.5, 129.2, 128.9, 127.9, 126.4, 125.3, 124.4, 123.6, 122.2,
120.5, 113.9, 111.2, 57.0, 55.9, 21.2. HRMS (ESI+) m/z
calculated for [(C19H18O3)H]+ 295.1329 found 295.1338.
3’,5’-dimethoxy-2,3,5-trimethyl-[1,1’-biphenyl-4,4’-diol]
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(17). White solid, 183−185 °C, 30.0 mg, 52% yield. H NMR
(400 MHz, CDCl3) δ 6.90 (1H, s), 6.48 (2H, s), 5.50 (1H, s), 4.69
(1H, s), 3.89 (6H, s), 2.27 (3H, s), 2.25 (3H, s), 2.16 (3H, s). 13
C
2-(2-(dimethylamino)naphthalen-1-yl)-6-methoxy-4-
NMR (150 MHz, CDCl3) δ 151.1, 146.5, 134.8, 133.9, 133.3,
133.0, 129.2, 122.3, 119.7, 106.4, 56.30, 56.28, 17.4, 15.8, 12.3.
IR νmas (film): 3491, 2937, 2843, 1607, 1405, 1206, 1087 cm-1.
HRMS (ESI+) m/z calculated for [(C17H20O4)H]+ 289.1434 found
289.1449.
methylphenol (11). Brown oil, 20.9 mg, 34% yield. 1H NMR (400
MHz, CDCl3) δ 8.61 (1H, br s), 7.88 (1H, d, J = 8.8 Hz), 7.81
(1H, d, J = 6.4 Hz), 7.80 (1H, d, J = 6.4 Hz), 7.45 (1H, d, J = 8.8
Hz), 7.40-7.30 (2H, m), 6.79 (1H, s), 6.75 (1H, s), 3.96 (3H, s),
2.72 (6H, s), 2.36 (3H, s). 13C NMR (150 MHz, CDCl3) δ 149.7,
146.8, 142.0, 133.6, 130.9, 129.0, 128.8, 128.2, 127.8, 126.3,
126.1, 125.3, 124.4, 117.7, 111.7, 56.0, 43.8, 21.3. IR νmas (film):
3526, 3424, 3057, 2933, 2843, 2786, 1595 cm-1. HRMS (ESI+)
m/z calculated for [(C20H21NO2)H]+ 308.1645 found 308.1655.
5-(tert-butyl)-3',5'-dimethoxy-[1,1'-biphenyl]-2,4'-diol
(18).10b 30.2 mg, 50% yield. 1H NMR (400 MHz, CDCl3) δ 7.30-
7.28 (1H, m), 7.23 (1H, d, J = 6.0 Hz), 6.94 (1H, d, J = 12.0 Hz),
6.67 (2H, s), 5.60 (1H, s), 5.19 (1H, s), 3.93 (6H, s), 1.34 (9H, s).
13C NMR (150 MHz, CDCl3) δ 150.1, 147.6, 143.4, 134.4, 128.4,
127.5, 126.8, 126.0, 115.1, 105.7, 56.37, 56.38, 34.2, 31.6.
HRMS (ESI+) m/z calculated for [(C18H22O4)H]+ 303.1591 found
303.1589.
3',5'-diisopropyl-3-methoxy-5-methyl-[1,1'-biphenyl]-2,4'-
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diol (12). Brown oil, 6.5 mg, 8% yield. H NMR (400 MHz,
CDCl3) δ 7.32-7.30 (4H, m), 7.27-7.23 (6H, m), 6.82 (2H, d, J =
8.0 Hz), 6.77 (2H, d, J = 8.0 Hz), 6.68 (1H, s), 6.66 (1H, s), 4.60
(4H, s), 3.85 (3H, s), 2.32 (3H, s). 13C NMR (150 MHz, CDCl3) δ
150.5, 148.9, 145.3, 144.6, 138.8, 133.2, 128.6, 126.8, 121.1,
119.1, 119.0, 113.9, 113.5, 56.0, 54.9, 21.2. IR νmas (film): 2922,
2849, 1503, 1267, 1224, 956 cm-1. HRMS (ESI+) m/z calculated
for [(C28H27NO2)H]+ 410.2115 found 410.2113.
3',5'-dimethoxy-3,5-dimethyl-[1,1'-biphenyl]-2,4'-diol (19).11b
35.1 mg, 64% yield. H NMR (400 MHz, CDCl3) δ 6.95 (1H, s),
6.87 (1H, s), 6.65 (2H, s), 5.58 (1H, s), 5.22 (1H, s), 3.92 (6H, s),
2.29 (3H, s), 2.28 (3H, s). 13C NMR (150 MHz, CDCl3) δ 148.3,
147.6, 134.3, 131.0, 129.2, 128.3, 127.8, 127.4, 124.3, 105.6,
56.4, 20.4, 16.2. HRMS (ESI+) m/z calculated for [(C16H18O4)H]+
275.1278 found 275.1275.
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2',3,4',5'-tetramethoxy-5-methyl-[1,1'-biphenyl]-2-ol (13).11b
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29.2 mg, 48% yield. H NMR (600 MHz, CDCl3) δ 6.85 (1H, s),
6.71 (1H, d, J = 1.8 Hz), 6.69 (1H, m), 6.65 (1H, s), 5.99 (1H, s),
3.94 (3H, s), 3.91 (3H, s), 3.86 (3H, s), 3.81 (3H, s), 2.33(3H, s).
HRMS (ESI+) m/z calculated for [(C17H20O5)H]+ 305.1384 found
305.1380.
3-(4-hydroxy-3,5-dimethoxyphenyl)-5,6,7,8-
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tetrahydronaphthalen-2-ol (20).11b 31.8 mg, 53% yield. H NMR
(400 MHz, CDCl3) δ 6.93 (1H, s), 6.71 (1H, s), 6.65 (2H, s), 5.56
(1H, s), 5.09 (1H, s), 3.91 (6H, s), 2.27 (4H, d, J = 16.0 Hz), 1.80
(4H, m). 13C NMR (150 MHz, CDCl3) δ 150.0, 147.5, 138.2,
134.2, 130.3, 129.2, 128.0, 125.8, 115.5, 105.6, 56.35, 56.33,
29.3, 28.5, 23.4, 23.1. HRMS (ESI+) m/z calculated for
[(C18H20O4)H]+ 301.1434 found 301.1430.
4-(2-(dimethylamino)naphthalen-1-yl)-2,6-dimethylphenol
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(14).6f 47.2 mg, 81% yield. H NMR (400 MHz, CDCl3) δ 7.78
(2H, t, J = 8.0 Hz), 7.55 (1H, d, J = 8.0 Hz), 7.42 (1H, d, J = 8.0
Hz), 7.35-7.27 (2H, m), 6.98 (2H, s), 4.66 (1H, s), 2.62 (6H, s),
2.32 (6H, s). 13C NMR (125 MHz, CDCl3) δ 150.9, 148.9, 134.1,
131.2, 130.8, 130.2, 129.7, 128.0, 127.6, 125.7, 125.5, 123.5,
122.6, 119.6, 44.2, 16.1. HRMS (ESI+) m/z calculated for
[(C20H21NO)H]+ 292.1696 found 292.1721.
3-methoxy-2',3',5,5'-tetramethyl-[1,1'-biphenyl]-2,4'-diol
(21). White solid, m.p: 165−167 °C. 13.6 mg, 25% yield. H
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NMR (400 MHz, CDCl3) δ 6.87 (1H, s), 6.70 (1H, s), 6.56 (1H,
s), 5.40 (1H, s), 4.67 (1H, s), 3.92 (3H, s), 2.32 (3H, s), 2.24 (6H,
s), 2.08 (3H, s). 13C NMR (150 MHz, CDCl3) δ 151.5, 146.2,
140.5, 134.2, 129.5, 129.3, 128.7, 128.4, 123.6, 122.1, 119.9,
110.4, 56.0, 21.1, 17.0, 15.8, 12.3. IR νmas (film): 3401, 2921,
2857, 1463, 1216, 1088 cm-1. HRMS (ESI+) m/z calculated for
[(C17H20O3)H]+ 273.1485 found 273.1494.
2-(2-(dimethylamino)naphthalen-1-yl)-4-methylphenol (15).
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Yellow oil, 16.7 mg, 30% yield. H NMR (400 MHz, CDCl3) δ
7.85 (1H, d, J = 8.0 Hz), 7.80 (1H, d, J = 8.0 Hz), 7.71 (1H, d, J
= 8.0 Hz), 7.36 (2H, d, J = 8.0 Hz), 7.04 (2H, d, J = 8.0 Hz), 6.72
(2H, d, J = 8.0 Hz), 2.94 (6H, s), 2.29 (3H, s). 13C NMR (150
MHz, CDCl3) δ 156.2, 130.6, 129.9, 129.3, 127.6, 126.4, 125.4,
123.6, 121.3, 119.2, 114.8, 42.8, 20.6. IR ν mas (film): 2917, 2848,
2789, 1598, 1500, 1373, 1228, 1211, 1165, 1074, 987, 809 cm-1.
HRMS (ESI+) m/z calculated for [(C19H19NO)H]+ 278.1539
found 278.1536.
3',5'-diisopropyl-3-methoxy-5-methyl-[1,1'-biphenyl]-2,4'-
diol (22). Yellow amorphous solid, 15.7 mg, 25% yield. 1H NMR
(400 MHz, CDCl3) δ 7.28 (2H, s), 6.75 (1H, s), 6.67 (1H, s), 5.62
(1H, s), 4.82 (1H, s), 3.92 (3H, s), 3.22-3.18 (2H, m), 2.34 (3H,
s), 1.32 (6H, s), 1.30 (6H, s). 13C NMR (125 MHz, CDCl3) δ
149.3, 146.6, 140.3, 133.3, 129.8, 128.9, 128.0, 124.5, 122.8,
110.2, 56.1, 27.3, 22.8, 21.1. IR νmas (film): 3533, 2960, 2936,
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