The Journal of Organic Chemistry
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8.20 (d, 1H, J = 7.7 Hz), 7.60−7.51 (m, 2H), 6.78 (s, 1H); 13C{1H}
NMR (DMSO-d6, 125 MHz): δ 151.5 (s), 147.0 (s), 128.5 (d and
s), 127.1 (d), 126.3 (s), 123.3 (d), 122.9 (d), 118.5 (s), 106.7 (d),
93.8 (s); HRMS (ESI) m/z: [M + H]+ calcd. for C11H8NO2
186.0555; found 186.0550.
6.92 (d, 1H, J = 8.7 Hz), 6.79 (d, 1H, J = 8.7 Hz), 4.02 (s, 3H), 3.98
(s, 3H), 2.67 (s, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 203.1
(s), 155.6 (s), 154.2 (s), 149.7 (s), 145.4 (s), 120.8 (s), 118.1 (s),
115.4 (s), 109.1 (d), 106.4 (d), 56.8 (q), 56.7 (q), 28.3 (q); HRMS
(ESI) m/z: [M + H]+ calcd. for C14H15O5 263.0919; found
263.0917.
1-(1,4-Dihydroxynaphthalen-2-yl)ethan-1-one (4c). Yellow solid
(93 mg, 46%); Rf 0.4 (hexanes−ethyl acetate, 2:1); mp 220−221 °C
(recryst. from hexanes−ethyl acetate, 1:1; Lit.11 205−207 °C); IR
Methyl 1,4-Dihydroxy-5,6-dimethoxy-2-naphthoate (4j). Yellow
solid (139 mg, 50%); Rf 0.6 (hexanes−ethyl acetate, 2:1); mp 130 °C
(recryst. from hexanes−ethyl acetate, 2:1); IR (ATR) 3356 (br),
1
(ATR) 3242 (br), 1636, 1614, 1595, 1574, 1520 cm−1; H NMR
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(CDCl3-DMSO-d6, 500 MHz): δ 13.52 (brs, 1H), 8.98 (brs, 1H),
8.39 (d, 1H, J = 8.6 Hz), 8.19 (d, 1H, J = 8.0 Hz), 7.65−7.61 (m,
1H), 7.55−7.51 (m, 1H), 7.05 (s, 1H), 2.63 (s, 3H); 13C{1H} NMR
(CDCl3-DMSO-d6, 125 MHz): δ 203.6 (s), 155.6 (s), 144.3 (s),
129.8 (s), 128.8 (d), 125.7 (d), 125.4 (s), 123.8 (d), 121.9 (d),
112.1 (s), 104.8 (d), 26.6 (q).
1643, 1611, 1506 cm−1; H NMR (CDCl3, 500 MHz): δ 11.52 (s,
1H), 9.08 (s, 1H), 8.21 (d, 1H, J = 9.2 Hz), 7.28 (d, 1H, J = 9.2 Hz),
7.10 (s, 1H), 4.06 (s, 3H), 4.03 (s, 3H), 3.97 (s, 3H); 13C{1H} NMR
(CDCl3, 125 MHz): δ 171.0 (s), 153.8 (s), 150.6 (s), 144.5 (s),
142.1 (s), 122.3 (s), 121.7 (d), 121.0 (s), 113.3 (d), 106.1 (d), 103.8
(s), 61.9 (q), 56.2 (q), 52.1 (q); HRMS (ESI) m/z: [M + H]+ calcd.
for C14H15O6 279.0869; found 279.0867.
Methyl 1,4-Dihydroxy-7,8-dimethoxy-2-naphthoate (4′j). Yellow
solid (67 mg, 24%); Rf 0.3 (hexanes−ethyl acetate, 2:1); mp 201 °C
(recryst. from hexanes−ethyl acetate, 1:2); IR (ATR) 3389 (br),
1665, 1638, 1601, 1578, 1526 cm−1; 1H NMR (CDCl3, 500 MHz): δ
11.94 (brs, 1H), 7.94 (d, 1H, J = 9.2 Hz), 7.40 (d, 1H, J = 9.2 Hz),
7.00 (s, 1H), 5.04 (brs, 1H), 4.00 (s, 3H), 3.96 (s, 3H), 3.95 (s,
3H); 13C{1H} NMR (CDCl3-DMSO-d6, 125 MHz): δ 170.6 (s),
153.7 (s), 150.0 (s), 145.1 (s), 144.1 (s), 125.5 (s), 120.3 (s), 118.6
(d), 116.0 (d), 105.2 (s), 102.4 (d), 61.3 (q), 56.2 (q), 51.6 (q);
HRMS (ESI) m/z: [M + H]+ calcd. for C14H15O6 279.0869; found
279.0869.
Methyl 1,4-Dihydroxy-6,7-dimethoxy-2-naphthoate (4d). White
solid (206 mg, 74%); Rf 0.3 (hexanes−ethyl acetate, 2:1); mp 192 °C
(recryst. from hexanes−ethyl acetate, 2:1); IR (ATR) 3295 (br),
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1774, 1663, 1636, 1609, 1589, 1518 cm−1; H NMR (CDCl3, 500
MHz): δ, 11.51 (brs, 1H) 7.66 (s, 1H), 7.43 (s, 1H), 7.00 (s, 1H),
5.02 (brs, 1H), 4.04 (s, 6H), 3.96 (s, 3H); 13C{1H} NMR (CDCl3,
125 MHz): δ 171.2 (s), 154.4 (s), 151.8 (s), 149.5 (s), 142.4 (s),
125.0 (s), 120.5 (s), 104.1 (d), 103.3 (s), 102.9 (d), 101.2 (d), 56.0
(q), 52.1 (q); HRMS (ESI) m/z: [M + H]+ calcd. for C14H15O6
279.0869; found 279.0863.
1,4-Dihydroxy-6,7-dimethoxy-2-naphthonitrile (4e). White solid
(169 mg, 69%); Rf 0.4 (hexanes−ethyl acetate, 1:1); mp 230 °C
(recryst. from hexanes−ethyl acetate, 1:5); IR (ATR) 3294 (br),
1,4-Dihydroxy-5,6-dimethoxy-2-naphthonitrile (4k) and 1,4-
Dihydroxy-7,8-dimethoxy-2-naphthonitrile (4′k) (2:1 Mixture).
White solid (213 mg, 87%); Rf 0.5 (hexanes−ethyl acetate, 1:1);
1H NMR (CDCl3, 500 MHz): δ 10.24 (brs, 0.33H), 9.36 (brs,
1
2228, 1620, 1589, 1528 cm−1; H NMR (CDCl3, 500 MHz): δ 9.48
(brs, 1H), 9.24 (brs, 1H), 7.60 (s, 1H), 7.49 (s, 1H), 6.69 (s, 1H),
4.02 (s, 3H), 4.00 (s, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ
150.5 (s), 150.2 (s), 149.3 (s), 145.3 (s), 124.1 (s), 121.0 (s), 118.6
(s), 105.5 (d), 102.2 (d), 101.5 (d), 91.2 (s), 55.70 (q), 55.65 (q);
HRMS (ESI) m/z: [M + H]+ calcd. for C13H12NO4 246.0766; found
246.0757.
1-(1,4-Dihydroxy-6,7-dimethoxynaphthalen-2-yl)ethan-1-one
(4f). Yellow solid (136 mg, 52%); Rf 0.35 (hexanes−ethyl acetate,
2:1); mp 236−238 °C (recryst. from hexanes−ethyl acetate, 2:1); IR
(ATR) 3294 (br), 1603, 1582 cm−1; 1H NMR (DMSO-d6, 500
MHz): δ 13.48 (brs, 1H), 9.66 (brs, 1H), 7.52 (s, 1H), 7.40 (s, 1H),
6.35 (s, 1H), 3.91 (s, 3H), 3.89 (s, 3H), 2.60 (s, 3H); 13C{1H} NMR
(DMSO-d6, 125 MHz): δ 204.2 (s), 153.5 (s), 151.8 (s), 149.3 (s),
143.7 (s), 125.7 (s), 119.6 (s), 111.6 (s), 103.9 (d), 102.6 (d), 101.6
(d), 55.5 (q), 55.4 (q), 26.8 (q); HRMS (ESI) m/z: [M + H]+ calcd.
for C14H15O5 263.0919; found 263.0913.
0.67H), 8.06 (d, 0.67H, J = 9.6 Hz), 7.98 (d, 0.33H, J = 9.5 Hz),
7.39 (d, 0.33H, J = 9.5 Hz), 7.34 (d, 0.67H, J = 9.6 Hz), 6.68 (s,
0.67H), 6.62 (s, 0.33H), 6.05 (brs, 0.67H), 5.23 (brs, 0.33H), 4.12
(s, 1H), 4.08 (s, 2H), 4.04 (s, 2H), 4.02 (s, 1H); 13C{1H} NMR
(DMSO-d6, 125 MHz): δ 151.34 (s), 151.31 (s), 151.1 (s), 149.1
(s), 146.3 (s), 146.2 (s), 142.8 (s), 142.7 (s), 123.8 (s), 122.1 (s),
122.0 (s), 120.8 (d), 119.9 (d), 118.1 (s), 118.0 (s), 117.8 (s), 117.2
(d), 115.2 (d), 108.1 (d), 104.5 (d), 92.2 (s), 92.0 (s), 62.2 (q), 61.9
(q), 56.7 (q), 56.5 (q); HRMS (ESI) m/z: [M + H]+ calcd. for
C13H12NO4 246.0766; found 246.0756.
1,4-Dihydroxy-5,6-dimethoxy-2-naphthonitrile (4k). White solid;
Rf 0.5 (hexanes−ethyl acetate, 1:1); mp > 300 °C (decomp.; recryst.
from ethyl acetate); IR (ATR) 3347 (br), 3273 (br), 2224, 1636,
1
1609, 1582, 1508 cm−1; H NMR (CDCl3-DMSO-d6, 500 MHz): δ
Methyl 1,4-Dihydroxy-5,8-dimethoxy-2-naphthoate (4g). Yellow
solid (220 mg, 79%); Rf 0.3 (hexanes−ethyl acetate, 2:1); mp 174−
175 °C (recryst. from hexanes−ethyl acetate, 1:1); IR (ATR) 3339
10.10 (brs, 1H), 9.25 (s, 1H), 8.11 (d, 1H, J = 9.3 Hz), 7.35 (d, 1H,
J = 9.3 Hz), 6.62 (s, 1H), 4.05 (s, 3H), 4.02 (s, 3H); 13C{1H} NMR
(CDCl3-DMSO-d6, 125 MHz): δ 150.8 (s), 149.8 (s), 145.7 (s),
142.0 (s), 121.6 (s), 120.9 (s), 120.7 (d), 117.4 (s), 113.9 (d), 107.6
(d), 91.6 (s), 61.5 (q), 55.9 (q).
1-(1,4-Dihydroxy-5,6-dimethoxynaphthalen-2-yl)ethan-1-one
(4l). Yellow solid (107 mg, 41%); Rf 0.6 (hexanes−ethyl acetate,
2:1); mp 170−172 °C (recryst. from hexanes−ethyl acetate, 1:1); IR
(ATR) 3350 (br), 1607, 1576, 1504 cm−1; 1H NMR (CDCl3-
DMSO-d6, 500 MHz): δ 13.58 (brs, 1H), 9.08 (brs, 1H), 8.25 (d,
1H, J = 9.3 Hz), 7.27 (d, 1H, J = 9.3 Hz), 6.96 (s, 1H), 4.07 (s, 3H),
4.03 (s, 3H), 2.62 (s, 3H); 13C{1H} NMR (CDCl3-DMSO-d6, 125
MHz): δ 203.0 (s), 154.6 (s), 151.1 (s), 143.7 (s), 141.9 (s), 122.3
(s), 121.5 (d), 120.6 (s), 113.6 (d), 111.0 (s), 106.1 (d), 61.4 (q),
55.9 (q), 26.2 (q); HRMS (ESI) m/z: [M + H]+ calcd. for C14H15O5
263.0919; found 263.0914.
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(br), 1670, 1638, 1611, 1570, 1516 cm−1; H NMR (CDCl3, 500
MHz): δ 11.76 (brs, 1H), 9.20 (brs, 1H), 7.25 (s, 1H), 6.89 (d, 1H,
J = 8.6 Hz), 6.78 (d, 1H, J = 8.6 Hz), 4.01 (s, 3H), 3.98 (s, 3H),
3.96 (s, 3H); 13C{1H} NMR (CDCl3, 125 MHz): δ 170.2 (s), 153.7
(s), 153.4 (s), 149.7 (s), 145.7 (s), 120.4 (s), 117.8 (s), 109.2 (d),
108.2 (d), 106.3 (d), 56.9 (q), 56.6 (q), 52.2 (q); HRMS (ESI) m/z:
[M + H]+ calcd. for C14H15O6 279.0869; found 279.0860.
1,4-Dihydroxy-5,8-dimethoxy-2-naphthonitrile (4h). White solid
(203 mg, 83%); Rf 0.45 (hexanes−ethyl acetate, 1:2); mp 214−215
°C (recryst. from hexanes−ethyl acetate, 1:5); IR (ATR) 3354 (br),
3302 (brs), 2214, 1616, 1516 cm−1; 1H NMR (CDCl3, 500 MHz): δ
9.93 (brs, 1H), 9.14 (brs, 1H), 6.83 (s, 1H), 6.82 (d, 1H, J = 8.7
Hz), 6.77 (d, 1H, J = 8.7 Hz), 4.04 (s, 3H), 4.03 (s, 3H); 13C{1H}
NMR (CDCl3-DMSO-d6, 125 MHz): δ 151.4 (s), 150.5 (s), 150.2
(s), 146.4 (s), 118.5 (s), 116.2 (s), 115.4 (s), 110.7 (d), 107.3 (d),
105.5 (d), 94.4 (s), 56.4 (q); HRMS (ESI) m/z: [M + H]+ calcd. for
C13H12NO4 246.0766; found 246.0758.
1-(1,4-Dihydroxy-7,8-dimethoxynaphthalen-2-yl)ethan-1-one
(4′l). Yellow solid (58 mg, 22%); Rf 0.3 (hexanes−ethyl acetate, 2:1);
mp 235−236 °C (recryst. from hexanes−ethyl acetate, 1:5); IR
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(ATR) 3393 (br), 1618, 1597, 1568, 1524 cm−1; H NMR (CDCl3-
DMSO-d6, 500 MHz): δ 13.63 (brs, 1H), 8.99 (brs, 1H), 7.99 (d,
1H, J = 9.2 Hz), 7.40 (d, 1H, J = 9.2 Hz), 6.95 (s, 1H), 3.99 (s, 3H),
3.96 (s, 3H), 2.65 (s, 3H); 13C{1H} NMR (CDCl3-DMSO-d6, 125
MHz): δ 202.2 (s), 154.9 (s), 149.9 (s), 145.9 (s), 144.0 (s), 125.8
(s), 120.3 (s), 118.5 (d), 116.9 (d), 113.6 (s), 103.1 (d), 61.0 (q),
1-(1,4-Dihydroxy-5,8-dimethoxynaphthalen-2-yl)ethan-1-one
(4i). Yellow solid (160 mg, 61%); Rf 0.3 (hexanes−ethyl acetate,
2:1); mp 154−155 °C (recryst. from hexanes−ethyl acetate, 1:2); IR
1
(ATR) 3362 (br), 1622, 1607, 1582, 1558, 1516 cm−1; H NMR
(CDCl3, 500 MHz): δ 13.44 (brs, 1H), 9.19 (brs, 1H), 7.11 (s, 1H),
G
J. Org. Chem. XXXX, XXX, XXX−XXX