The Journal of Organic Chemistry
Article
5-bromosalicylaldehyde (1e), and 2-hydroxy-1-naphthaldehyde (1j)
were purchased from commercial suppliers. The other substituted
salicylaldehydes (1b,15a 1c,15a 1d,15b 1f,15c 1g,16a 1i,16b 1k,16c 1l,17a
and 1m17b) were prepared by following literature-known procedures.
General Procedure for Deformylative Coupling Reactions.
The deformylative coupling reaction was performed by charging a dry
Schlenk tube with salicylaldehyde (1a) (61 mg, 0.5 mmol), ethyl
acrylate (2a) (200 mg, 2 mmol), Rh(CO)2(acac) (6.4 mg, 0.025
mmol), and DMF (2 mL) solvent. This mixture was stirred at 120 °C
in a preheated oil bath for 3 h. At the end, the contents were brought
to room temperature (rt), quenched with dil. HCl, and extracted with
ethyl acetate (30 mL). The organic extract was washed with water (15
mL) and brine (15 mL), dried with anhydrous MgSO4, and
concentrated. The crude product was purified by silica gel column
chromatography using ethyl acetate/hexane as eluent. The product 3a
was obtained as a colorless solid (89 mg, 92%).
CDCl3): δ 8.84 (s, 1H), 8.12−8.03 (m, 2H), 7.88 (dd, J = 8.5, 2.2 Hz,
1H), 7.00 (d, J = 8.5 Hz, 1H), 6.78 (d, J = 16.2 Hz, 1H), 4.32 (q, J =
7.1 Hz, 2H), 2.59 (s, 3H), 1.37 (t, J = 7.1 Hz, 3H) ppm; 13C{1H}
NMR (100 MHz, CDCl3): δ 197.4, 168.9, 160.5, 140.4, 132.1, 130.7,
129.9, 121.8, 119.6, 116.7, 61.2, 26.5, 14.4 ppm; IR (KBr, cm−1):
3216, 2925, 1678, 1633, 1592, 1278, 1179, 832; HRMS (ESI+): calcd
for C13H15O4 [M + H]+ 235.0970, found 235.0973.
(E)-Ethyl 3-(2-Hydroxy-4-methoxyphenyl)acrylate (3g).18b Color-
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less solid (71 mg, 64%); mp 118−120 °C; H NMR (400 MHz,
CDCl3): δ 8.00 (d, J = 16.1 Hz, 1H), 7.39 (d, J = 8.7 Hz, 1H), 7.29 (s,
1H), 6.55 (d, J = 16.1 Hz, 1H), 6.48 (dd, J = 8.6, 2.4 Hz, 1H), 6.42
(d, J = 2.4 Hz, 1H), 4.28 (q, J = 7.1 Hz, 2H), 3.79 (s, 3H), 1.35 (t, J =
7.1 Hz, 3H) ppm; 13C{1H} NMR (125 MHz, CDCl3): δ 169.3, 162.7,
157.4, 141.0, 130.6, 115.5, 115.1, 107.1, 102.0, 60.7, 55.5, 14.5 ppm;
IR (KBr, cm−1): 3348, 2964, 1674, 1612, 1588, 1447, 1430, 1311,
1188, 1208, 1110, 1032, 843, 810; HRMS (ESI+): calcd for C12H15O4
[M + H]+ 223.0970, found 223.0970.
Characterization Data for the Products (3a−3n, 1A, 1B, and
4a−4d). (E)-Ethyl 3-(2-Hydroxyphenyl)acrylate (3a).18a Colorless
solid (89 mg, 92%); mp 64−65 °C; 1H NMR (400 MHz, CDCl3): δ
8.05 (d, J = 16.2 Hz, 1H), 7.47 (dd, J = 7.8, 1.6 Hz, 1H), 7.26−7.21
(m, 1H), 6.92 (td, J = 7.4, 1.0 Hz, 1H), 6.86 (dd, J = 8.1, 1.0 Hz, 1H),
6.69 (s, 1H), 6.65 (d, J = 16.2 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 1.35
(t, J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 168.6,
155.6, 140.8, 131.6, 129.3, 121.9, 120.8, 118.6, 116.6, 60.8, 14.6 ppm;
IR (KBr, cm−1): 3440, 3059, 2920, 1731, 1622, 1607, 1564, 1454,
1400, 1179, 1121, 929, 890, 828, 753; HRMS (EI+): calcd for
C11H12O3 [M]+ 192.0786, found 192.0782.
(E)-Ethyl 3-(2-Hydroxy-3-methoxyphenyl)acrylate (3h). Colorless
solid (91 mg, 82%); mp 65−66 °C; 1H NMR (400 MHz, CDCl3): δ
7.94 (d, J = 16.2 Hz, 1H), 7.09−7.06 (m, 1H), 6.86−6.83 (m, 2H),
6.60 (d, J = 16.2 Hz, 1H), 6.20 (s, 1H), 4.26 (q, J = 7.1 Hz, 2H), 3.90
(s, 3H), 1.33 (t, J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (100 MHz,
CDCl3): δ 167.6, 146.9, 145.4, 139.6, 121.01, 120.95, 119.7, 119.4,
111.8, 60.5, 56.3, 14.5 ppm; IR (KBr, cm−1): 3384, 2984, 2936, 1702,
1630, 1588, 1482, 1366, 1261, 1178, 1073, 1034, 781; HRMS (EI+):
calcd for C12H14O4 [M]+ 222.0892, found 222.0882.
(E)-Ethyl 3-(2-Hydroxy-3,4,5-trimethoxyphenyl)acrylate (3i). Col-
(E)-Ethyl 3-(2-Hydroxy-5-methylphenyl)acrylate (3b).18a Color-
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orless solid (106 mg, 75%); mp 116−118 °C; H NMR (400 MHz,
1
less solid (91 mg, 88%); mp 112−114 °C; H NMR (400 MHz,
CDCl3): δ 7.87 (d, J = 16.1 Hz, 1H), 6.72 (s, 1H), 6.50 (d, J = 16.1
Hz, 1H), 6.02 (s, 1H), 4.26 (q, J = 7.1 Hz, 2H), 3.96 (s, 3H), 3.92 (s,
3H), 3.82 (s, 3H), 1.33 (t, J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 167.7, 146.8, 144.0, 143.7, 140.5, 139.5, 118.0,
115.3, 106.3, 61.5, 61.2, 60.5, 56.5, 14.5 ppm; IR (KBr, cm−1): 3373,
2992, 2942, 2838, 1703, 1631, 1493, 1468, 1423, 1290, 1256, 1132,
1084, 842, 621; HRMS (ESI+): calcd for C14H19O6 [M + H]+
283.1182, found 283.1183.
CDCl3): δ 8.00 (dd, J = 16.2, 2.4 Hz, 1H), 7.26 (m, 1H), 7.03 (dd, J =
8.2, 2.2 Hz, 1H), 6.75 (dd, J = 8.2, 1.7 Hz, 1H), 6.61 (dd, J = 16.2, 1.9
Hz, 1H), 6.48 (s, 1H), 4.28 (q, J = 7.1 Hz, 2H), 2.27 (s, 3H), 1.35 (t,
J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ 168.6,
153.4, 140.8, 132.2, 130.0, 129.6, 121.5, 118.3, 116.4, 60.8, 20.6, 14.5
ppm; IR (KBr, cm−1): 3274, 2978, 1671, 1621, 1611, 1505, 1368,
1329, 1257, 1196, 1159, 1026, 988, 822, 681; HRMS (EI+): calcd for
C12H14O3 [M]+ 206.0943, found 206.0941.
(E)-Ethyl 3-(2-Hydroxynaphthalen-1-yl)acrylate (3j). Colorless
solid (38 mg, 31%); mp 132−134 °C; 1H NMR (400 MHz,
CDCl3): δ 8.35 (d, J = 16.3 Hz, 1H), 8.04 (d, J = 9.4 Hz, 1H), 7.78−
7.74 (m, 2H), 7.52 (ddd, J = 8.4, 6.9, 1.4 Hz, 1H), 7.40−7.35 (m,
1H), 7.16 (d, J = 8.9 Hz, 1H), 6.81 (d, J = 16.3 Hz, 1H), 6.60 (s, 1H),
4.36 (q, J = 7.1 Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H) ppm; 13C{1H} NMR
(100 MHz, CDCl3): δ 168.1, 153.3, 138.6, 132.9, 131.7, 129.0, 128.8,
127.6, 124.0, 123.4, 123.1, 118.2, 114.0, 61.0, 14.5 ppm; IR (KBr,
cm−1): 3067, 1728, 1565, 1279, 1177, 814, 748; HRMS (ESI−): calcd
for C15H13O3 [M − H]− 241.0865, found 241.0869.
(E)-Ethyl 3-(5-Fluoro-2-hydroxyphenyl)acrylate (3c). Colorless
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solid (87 mg, 83%); mp 88−90 °C; H NMR (400 MHz, CDCl3):
δ 8.03 (d, J = 16.2 Hz, 1H), 7.16 (dd, J = 9.2, 3.0 Hz, 1H), 7.07 (s,
1H), 6.95 (ddd, J = 8.8, 7.8, 3.0 Hz, 1H), 6.82 (dd, J = 8.9, 4.6 Hz,
1H), 6.59 (d, J = 16.2 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 1.36 (t, J =
7.1 Hz, 3H) ppm; 13C{1H} NMR (125 MHz, CDCl3): δ 168.5, 156.9
(d, JC−F = 237.1 Hz), 151.7 (d, JC−F = 1.9 Hz), 139.8 (d, JC−F = 2.2
Hz), 122.8 (d, JC−F = 7.5 Hz), 119.3, 118.2 (d, JC−F = 23.5 Hz), 117.5
(d, JC−F = 8.0 Hz), 114.5 (d, JC−F = 23.11 Hz), 61.1, 14.4 ppm; IR
(KBr, cm−1): 3393, 3223, 2980, 1687, 1633, 1508, 1444, 1184, 1031,
861, 782, 752; HRMS (ESI+): calcd for C11H12FO3 [M + H]+
211.0770, found 211.0776.
(E)-Methyl 3-(2-Hydroxyphenyl)acrylate (3k).19a Colorless solid
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(73 mg, 82%); mp 126−128 °C; H NMR (400 MHz, CDCl3): δ
8.06 (d, J = 16.2 Hz, 1H), 7.46 (d, J = 8.8 Hz, 1H), 7.26−7.22 (m,
1H), 6.92 (t, J = 7.4 Hz, 1H), 6.87 (d, J = 8.1 Hz, 1H), 6.82 (s, 1H),
6.66 (d, J = 16.2 Hz, 1H), 3.83 (s, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 169.0, 155.5, 141.0, 131.6, 129.4, 121.8, 120.9,
118.2, 116.6, 52.0 ppm; IR (KBr, cm−1): 3389, 3034, 2849, 1694,
1630, 1458, 1331, 1259, 1229, 1200, 1178, 991, 761, 754; HRMS
(EI+): calcd for C10H10O3 [M]+ 178.0630, found 178.0637.
(E)-Ethyl 3-(5-Chloro-2-hydroxyphenyl)acrylate (3d). Colorless
solid (84 mg, 74%); mp 102−104 °C; 1H NMR (400 MHz, CDCl3):
δ 7.99 (d, J = 16.2 Hz, 1H), 7.49 (s, 1H), 7.43 (d, J = 2.6 Hz, 1H),
7.18 (dd, J = 8.6, 2.6 Hz, 1H), 6.83 (d, J = 8.7 Hz, 1H), 6.64 (d, J =
16.2 Hz, 1H), 4.30 (q, J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H) ppm;
13C{1H} NMR (100 MHz, CDCl3): δ 168.7, 154.3, 139.7, 131.2,
128.5, 125.6, 123.2, 119.4, 117.9, 61.2, 14.4 ppm; IR (KBr, cm−1):
3346, 2989, 1894, 1684, 1625, 1582, 1494, 1413, 1307, 1183, 1034,
982, 864, 820; HRMS (EI+): calcd for C11H11ClO3 [M]+ 226.0397,
found 226.0380.
(E)-Ethyl 3-(5-Bromo-2-hydroxyphenyl)acrylate (3e). Colorless
solid (119 mg, 88%); mp 108−110 °C; 1H NMR (400 MHz, CDCl3):
δ 7.98 (d, J = 16.2 Hz, 1H), 7.57−7.54 (m, 2H), 7.31 (dd, J = 8.6, 2.4
Hz, 1H), 6.78 (d, J = 8.6 Hz, 1H), 6.64 (d, J = 16.2 Hz, 1H), 4.30 (q,
J = 7.1 Hz, 2H), 1.36 (t, J = 7.1 Hz, 3H) ppm; 13C{1H} NMR (100
MHz, CDCl3): δ 168.9, 154.9, 139.8, 134.1, 131.5, 123.8, 119.3,
118.3, 112.6, 61.2, 14.4 ppm; IR (KBr, cm−1): 3350, 2987, 2917,
2849, 1685, 1624, 1308, 1185, 981, 863, 822, 634; HRMS (ESI+):
calcd for C11H12BrO3 [M + H]+ 270.9970, found 270.9977.
(E)-Ethyl 3-(5-Acetyl-2-hydroxyphenyl)acrylate (3f). Colorless
solid (65 mg, 55%); mp 152−154 °C; 1H NMR (400 MHz,
(E)-n-Butyl 3-(2-Hydroxyphenyl)acrylate (3l).19b Colorless solid
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(93 mg, 84%); mp 90−92 °C; H NMR (400 MHz, CDCl3): δ 8.06
(d, J = 16.2 Hz, 1H), 7.47 (dd, J = 7.8, 1.4 Hz, 1H), 7.25−7.22 (m,
1H), 7.06 (s, 1H), 6.93−6.86 (m, 2H), 6.67 (d, J = 16.2 Hz, 1H),
4.25 (t, J = 6.7 Hz, 2H), 1.71−1.67 (m, 2H), 1.45 (h, J = 7.4 Hz, 2H),
0.97 (t, J = 7.4 Hz, 3H) ppm; 13C{1H} NMR (100 MHz, CDCl3): δ
168.9, 155.7, 141.0, 131.6, 129.4, 121.9, 120.7, 118.4, 116.6, 64.8,
30.9, 19.3, 13.9 ppm; IR (KBr, cm−1): 3317, 2960, 2934, 2896, 2871,
1911, 1692, 1626, 1603, 1588, 1503, 1455, 1318, 1268, 1190, 1113,
993, 905, 875, 756, 676, 601; HRMS (EI+): calcd for C13H16O3 [M]+
220.1099, found 220.1084.
(E)-tert-Butyl 3-(2-Hydroxyphenyl)acrylate (3m). Colorless solid
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(90 mg, 81%); mp 97−99 °C; H NMR (400 MHz, CDCl3): δ 7.99
(d, J = 16.2 Hz, 1H), 7.45 (dd, J = 7.8, 1.6 Hz, 1H), 7.24−7.20 (m,
1H), 7.08 (d, J = 7.2 Hz, 1H), 6.92−6.84 (m, 2H), 6.58 (d, J = 16.2
E
J. Org. Chem. XXXX, XXX, XXX−XXX