The Journal of Organic Chemistry
Article
1H), 6.89−6.82 (m, 4H), 5.98 (d, J = 12.4 Hz, 1H), 5.05 (s, 2H),
3.77 (s, 6H); 13C{1H} NMR (100 MHz, CDCl3): δ 166.2, 159.6,
157.2, 139.4, 130.8, 130.4, 130.2, 128.1, 124.1, 120.0, 119.8, 113.9,
110.3, 65.8, 55.4, 55.3. Anal. Calcd for C18H18O4: C, 72.47; H, 6.08.
Found: C, 72.14; H, 6.11.
(4-Methoxyphenyl)methyl Picolinate (20j). It was obtained as
yellow oil (0.516 g, 83%) and purified by silica gel chromatography
(50% ethyl acetate/50% hexanes). TLC Rf = 0.30 (50% ethyl acetate/
50% hexanes); IR (film, cm−1) νmax: 3057, 3005, 2957, 2837, 1717;
1H NMR (300 MHz, CDCl3): δ 8.76 (d, J = 7.2 Hz, 1H), 8.12 (d, J =
8.7 Hz, 1H), 7.85−7.79 (m, 1H), 7.48−7.42 (m, 3H), 6.90 (d, J = 8.7
Hz, 2H), 5.40 (s, 2H), 3.81 (s, 3H); 13C{1H} NMR (75 MHz,
CDCl3): δ 165.2, 159.8, 150.0, 148.2, 137.0, 130.6, 127.9, 127.0,
125.3, 114.0, 67.4, 55.3. Anal Calcd for C14H13NO3: C, 69.12; H,
5.39; N, 5.76. Found C, 69.52; H, 5.65; N, 5.73.
(2,4-Dimethoxyphenyl)methyl Benzoate (21a). It was obtained as
clear oil (0.062 g, 90%) and purified by silica gel chromatography (6%
ethyl acetate/94% hexanes). TLC Rf = 0.29 (10% ethyl acetate/90%
hexane); IR (film, cm−1) νmax: 3003, 2837, 1721, 1275, 712; 1H NMR
(400 MHz, CDCl3): δ 8.05 (d, J = 7.2 Hz, 2H), 7.51 (t, J = 7.2 Hz,
1H), 7.39 (t, J = 8.0 Hz, 2H), 7.34−7.32 (m, 1H), 6.49−6.46 (m,
2H), 5.34 (s, 2H), 3.81 (s, 3H), 3.80 (s, 3H); 13C{1H} NMR (100
MHz, CDCl3): δ 166.7, 161.3, 159.0, 132.8, 131.2, 130.6, 129.7,
128.3, 116.9, 104.1, 98.6, 62.1, 55.5, 55.4. Anal. Calcd for C16H16O4:
C, 70.58; H, 5.92. Found: C, 70.57; H, 5.87.
80%) and purified by silica gel chromatography (15% ethyl acetate/
85% hexanes). TLC Rf = 0.37 (40% ethyl acetate/60% hexanes); IR
(film, cm−1) νmax: 3054, 2985, 1709, 1421, 1261, 739; 1H NMR (300
MHz, CD3OD): δ 7.26−7.16 (m, 6H), 6.56 (d, J = 2.2 Hz, 1H), 6.50
(dd, J = 8.3, 2.3 Hz, 1H), 5.11 (q, J = 12.1 Hz, 2H), 4.38 (q, J = 6.0
Hz, 1H), 3.84 (s, 3H), 3.82 (s, 3H), 3.10 (dd, J = 13.9, 5.6 Hz, 1H),
2.91 (dd, J = 13.7, 8.6 Hz, 1H), 1.39 (s, 9H); 13C{1H} NMR (75
MHz, CD3OD): δ 172.3, 161.7, 159.0, 156.4, 136.9, 131.2, 128.9,
128.0, 126.4, 116.0, 104.1, 97.9, 79.2, 62.1, 55.2, 54.6, 54.4, 37.3, 27.3.
Anal Calcd for C23H29NO6: C, 66.49; H, 7.04; N, 3.37. Found: C,
66.20; H, 6.93; N, 3.76.
(2,4-Dimethoxyphenyl)methyl But-3-enoate (21g). It was ob-
tained as clear oil (0.163 g, 73%) and purified by silica gel
chromatography (15% ethyl acetate/85% hexanes). TLC Rf = 0.40
(15% ethyl acetate/85% hexanes); IR (film, cm−1) νmax: 2963, 2838,
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2616, 1464, 1371, 1209, 739; H NMR (300 MHz, CDCl3): δ 7.23
(d, J = 8.9 Hz, 1H), 6.46 (hextet, J = 2.4 Hz, 2H), 6.00−5.87 (m,
1H), 5.18−5.11 (m, 4H), 3.81 (s, 3H), 3.80 (s, 3H), 3.11 (dt, J = 6.9,
1.4 Hz, 2H); 13C{1H} NMR (75 MHz, CDCl3): δ 171.6, 161.3, 159.0,
131.4, 130.5, 118.4, 116.7, 104.1, 98.6, 61.9, 55.5, 55.4, 39.2. Anal.
Calcd for C13H16O4: C, 66.09; H, 6.83. Found: C, 65.91; H, 6.47.
(2,4-Dimethoxyphenyl)methyl Cinnamate (21h). It was obtained
as viscous oil (0.139 g, 88%) and purified by silica gel
chromatography (4% ethyl acetate/98% hexanes). TLC Rf = 0.38
(20% ethyl acetate/80% hexanes); IR (film, cm−1) νmax: 1708, 1510,
1161, 737. 1H NMR (400 MHz, CDCl3): δ 7.70 (d, J = 16.1 Hz, 1H),
7.51−7.49 (m, 2H), 7.37−7.35 (m, 3H), 7.30 (d, J = 8.9 Hz, 1H),
6.49−6.51−6.43 (m, 3H), 5.23 (s, 2H), 3.83 (s, 3H), 3.81 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 167.1, 161.3, 159.1, 144.7,
(2,4-Dimethoxyphenyl)methyl 2,2-Diphenylacetate (21b). It was
obtained as clear oil (0.120 g, 88%) and purified by silica gel
chromatography (15% ethyl acetate/85% hexanes). TLC Rf = 0.27
(20% ethyl acetate/80% hexanes); IR (film, cm−1) νmax: 1731, 1616,
1
1209, 1035, 701; H NMR (400 MHz, CDCl3): δ 7.30−7.23 (m,
134.6, 131.5, 130.2, 128.9, 128.1, 118.4, 116.8, 104.1, 98.6, 61.8, 55.5,
55.4. Anal. Calcd for C18H18O4: C, 72.47; H, 6.08. Found: C, 72.20;
H, 5.71.
10H), 7.15 (d, J = 8.7 Hz, 1H), 6.42−6.39 (m, 2H), 5.16 (s, 2H),
5.04 (s, 1H), 3.79 (s, 3H), 3.70 (s, 3H); 13C{1H} NMR (100 MHz,
CDCl3): δ 172.4, 161.3, 159.0, 138.9, 131.3, 128.7, 128.5, 127.1,
116.6, 103.9, 98.5, 62.6, 57.1, 55.4, 55.3. Anal. Calcd for C23H22O4: C,
76.22; H, 6.12. Found: C, 76.08; H, 6.10.
(2,4-Dimethoxyphenyl)methyl (2Z)-3-(2-Methoxyphenyl)prop-2-
enoate (21i). It was obtained as clear oil (0.170 g, 92%) and purified
by silica gel chromatography (20% ethyl acetate/80% hexanes). TLC
Rf = 0.29 (20% ethyl acetate/80% hexanes); IR (film, cm−1) νmax
:
(2,4-Dimethoxyphenyl)methyl 2-Methyl-2-phenylpropanoate
(21c). It was obtained as clear oil (0.200 g, 85%) and purified by
silica gel chromatography (8% ethyl acetate/92% hexanes). TLC Rf =
0.45 (10% ethyl acetate/90% hexanes); IR (film, cm−1) νmax: 3061,
3054, 2986, 2839, 1717, 1616, 1488, 1209, 1159, 739, 705; 1H NMR
(400 MHz, CDCl3): δ 7.57 (d, J = 7.5 Hz, 1H), 7.31−7.26 (m, 1H),
7.18−7.15 (m, 2H), 6.90−6.85 (m, 2H), 6.44−6.41 (m, 2H), 6.01 (d,
J = 12.5 Hz, 1H), 5.14 (s, 2H), 3.81 (s, 6H), 3.78 (s, 3H); 13C{1H}
NMR (100 MHz, CDCl3): δ 166.3, 161.2, 158.9, 157.2, 138.9, 131.3,
130.8, 130.3, 124.1, 120.00, 119.94, 116.8, 110.3, 104.0, 98.5, 61.3,
55.41, 55.40. Anal. Calcd for C19H20O5: C, 69.50; H, 6.14. Found: C,
69.87; H, 6.47.
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2936, 1718, 1612, 1508, 1206, 1098, 1029, 731, 697; H NMR (400
MHz, CDCl3): δ 7.26−7.11 (m, 5H), 6.98 (d, J = 7.8 Hz, 1H), 6.32−
6.30 (m, 2H), 5.00 (s, 2H), 3.71 (s, 3H), 3.63 (s, 3H), 1.50 (s, 6H);
13C{1H} NMR (75 MHz, CDCl3): δ 176.6, 161.0, 158.7, 144.9, 130.5,
128.2, 126.5, 125.8, 117.1, 103.8, 98.4, 62.1, 55.4, 55.3, 46.7, 26.5.
Anal. Calcd for C19H22O4: C, 72.59; H, 7.05. Found: C, 72.36; H,
7.17.
(2,4-Dimethoxyphenyl)methyl Picolinate (21j). It was obtained as
yellow oil (0.150 g, 83%) and purified by silica gel chromatography
(50% ethyl acetate/50% hexanes). TLC Rf = 0.25 (50% ethyl acetate/
50% hexanes); IR (film, cm−1) νmax: 2964, 1721, 1616, 1377, 927; 1H
NMR (400 MHz, CDCl3): δ 8.76 (dd, J = 4.7 Hz, 0.7 Hz, 1H), 8.10
(d, J = 7.8 Hz, 1H), 7.79 (td, J = 7.8, 1.7 Hz, 1H), 7.41 (ddd, J = 7.6,
4.8, 1.1 Hz 1H), 7.34 (d, J = 9.0 Hz, 1H), 6.48−6.46 (m, 2H), 5.43 (s,
2H), 3.82 (s, 3H), 3.80 (s, 3H); 13C{1H} NMR (75 MHz, CDCl3): δ
165.2, 161.4, 159.1, 150.0, 148.5, 136.8, 131.6, 126.7, 125.2, 116.5,
104.1, 98.6, 62.9, 55.5, 55.4. Anal. Calcd for C15H15NO4: C, 65.92; H,
5.53; N, 5.13. Found: C, 66.17; H, 5.54; N, 5.44.
(2,4-Dimethoxyphenyl)methyl 2-Bromododecanoate (21d). It
was obtained as clear oil (0.099 g, 81%) and purified by silica gel
chromatography (5% ethyl acetate/95% hexane). TLC Rf = 0.57
(20% ethyl acetate/80% hexanes); IR (film, cm−1) νmax: 3054, 1422,
1
1265, 1038, 896, 739. H NMR (400 MHz, CDCl3): δ 7.24 (s, 1H),
6.48−6.46 (m, 2H), 5.18 (s, 2H) 4.22 (t, J = 7.4 Hz, 1H), 3.81 (s,
6H), 2.11−1.92 (m, 2H), 1.49−1.19 (m, 16H), 0.88 (t, J = 6.6 Hz,
3H); 13C{1H} NMR (100 MHz, CDCl3): δ 169.9, 161.5, 159.0,
131.4, 116.1, 104.0, 98.6, 63.1, 55.4, 55.4, 46.4, 35.0, 31.9, 29.6, 29.5,
29.3, 29.3, 28.9, 27.2, 22.7, 14.1. Anal. Calcd for C21H33BrO4: C,
58.74; H, 7.75. Found: C, 58.57; H, 7.65.
3,4-Dimethoxybenzyl Benzoate (22a).59 It was obtained as clear
oil (0.17 g, 96%) and purified by silica gel chromatography (5% ethyl
acetate/95% hexanes). TLC Rf = 0.40 (20% ethyl acetate/80%
( )-(2,4-Dimethoxyphenyl)methyl-2-hydroxy-2-phenylacetate
(21e). It was obtained as a white amorphous solid (0.150 g, 94%) and
purified by silica gel chromatography (50% ethyl acetate/50%
hexanes). TLC Rf = 0.37 (50% ethyl acetate/50% hexanes); mp =
1
hexane); H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 7.2 Hz, 2H),
7.52 (t, J = 7.6 Hz, 1H), 7.40 (t, J = 7.6 Hz, 2H), 7.03−6.97 (m, 2H),
6.85 (d, J = 8.0 Hz, 1H), 5.29 (s, 2H), 3.88 (s, 3H), 3.86 (s, 3H);
13C{1H} NMR (100 MHz, CDCl3): δ 166.5, 149.1, 149.0, 133.0,
130.2, 129.7, 128.6, 128.4, 121.3, 111.9, 111.1, 66.8, 55.9.
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290−292 °C; IR (film, cm−1) νmax: 3054, 2835, 1729, 1274, 762; H
NMR (400 MHz, CDCl3): δ 7.41−7.39 (m, 2H), 7.34−7.28 (m, 3H),
7.07 (d, J = 8.9 Hz, 1H), 6.39 (br s, 2H), 5.16−5.15 (m, 3H), 3.78 (s,
3H), 3.67 (s, 3H), 3.54 (br s, 1H); 13C{1H} NMR (100 MHz,
CDCl3): δ 173.6, 161.5, 159.0, 138.5, 131.2, 128.4, 128.3, 126.6,
115.8, 103.9, 98.5, 72.9, 63.5, 55.4, 55.3. Anal. Calcd for C17H18O5: C,
67.54; H, 6.00. Found: C, 67.72; H, 5.87.
(Furan-2-yl)methyl Benzoate (24a).60 It was obtained as yellow
oil (0.127 g, 96%) and purified by silica gel chromatography (1% ethyl
acetate/99% hexane). TLC Rf = 0.46 (10% ethyl acetate/90%
1
hexane); H NMR (400 MHz, CDCl3): δ 8.06 (d, J = 8.2 Hz, 2H),
7.57−7.53 (m, 1H), 7.45−7.41 (m, 3H), 6.49 (d, J = 3.2 Hz, 1H),
( )-(2,4-Dimethoxyphenyl)methyl-2-[(tert-butoxycarbonyl)-
amino]phenylpropionate (21f). It was obtained as clear oil (0.101 g,
6.39−6.38 (m, 1H), 5.31 (s, 2H); 13C{1H} NMR (100 MHz,
H
J. Org. Chem. XXXX, XXX, XXX−XXX