PleNaeswe dJoounrnoatlaodfjCuhstemmiastrrgyins
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mmol), malonic acid 50 (274.7 mg, 2.6 mmol) and piperidine (0.1 dimethylchroman-6'-yl) acrylate (60) was obtained (514.4 mg, 76%
o
mL), 3-(5',7'-dimethoxy-2', 2'-dimethylchroman-8'-yl) acrylic acid yield) as a white solid (mp: 155 C. IR specDtrOuIm: 10(.K10B3r9),/Dc0mNJ:022192659C,
(53) was obtained (515 mg, 80% yield) as a light brown solid (mp: 130 2932, 1701 (C=O), 1624, 1570, 1444, 1320, 1235, 1160. 1H NMR (300
oC). IR spectrum (KBr), cm-1: 3420, 2928, 1678 (C=O), 1601, 1465, MHz, CDCl3) δ ppm: 1.38 (6H, s, 2 x CH3), 1.81 (2H, t, J = 6.6 Hz, C-
1353, 1305, 1252. 1H NMR (300 MHz, CDCl3) δ ppm: 1.37 (6H, s, 2 x 3'H), 2.73 (2H, t, J = 6.6 Hz, C-4'H), 3.84 (3H, s, OCH3), 6.36 (1H, s, C-
CH3), 1.76 (2H, t, J = 6.6 Hz, C-3'H), 2.57 (2H, t, J = 6.6 Hz, C-4'H) , 3.86 8'H), 6.60 (1H, d, J = 15.9 Hz, C-2H), 7.14-7.26 (4H, m, C-5', C-4'', C-3''
(6H, s, 2 x OCH3), 6.04 (1H, s, C-6'H), 6.80 (1H, d, J = 15.9 Hz, C-2H), & C-5''), 7.39-7.41 (2H, m, C-2'' & C-6''), 8.05 (1H, d, J = 15.9 Hz, C-
8.22 (1H, d, J = 15.9 Hz, C-3H). 13C NMR (75.5 MHZ, CDCl3) δ ppm: 3H). 13C NMR (75.5 MHZ, CDCl3) δ ppm: 21.53 (C-4'), 26.91 (2 x CH3),
16.67 (C-4'), 26.62 & 26.72 (2 x CH3), 31.78 (C-3'), 55.35 & 55.66 (2 x 32.78 (C-3'), 55.51 (OCH3), 75.40 (C-2'), 100.18 (C-8'), 113.24 (C-10'),
OCH3), 75.38 (C-2'), 86.59 (C-6'), 102.51 (C-10'), 105.30 (C-8'), 115.89 114.43 (C-2), 115.62 (C-6'), 121.80 (C-3'' & C-5''), 125.46 (C-4''),
(C-2), 127.06 (C-3), 155.47 (C-9'), 159.76 (C-7'), 160.16 (C-5'), 174.65 128.51 (C-2'' & C-6''), 130.91 (C-5'), 142.34 (C-3), 151.12 (C-1''),
(C=O). HRMS: found 315.1196 [M+Na]+; calculated 315.1203 for 157.58 (C-9'), 158.68 (C-7'), 166.46 (C=O). HRMS: found 339.1591
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C16H20O5 Na.
[M+H]+; calculated 339.1591 for C21H23O4.
General procedure of the synthesis of chromanyl acrylates 58-69
(E)-4-Methoxyphenyl 3-(7'- methoxy-2', 2'-dimethylchroman-
6'-yl) acrylate (61). Following the general procedure, with carboxylic
acid 51 (524.6 mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol)
and 4-methoxyphenol 57 (1.2 g, 10 mmol), (E)-4-methoxyphenyl 3-
(7'- methoxy-2', 2'-dimethylchroman-6'-yl) acrylate (61) was
To a stirred suspension of carboxylic acid 51-53 (2 mmol) in the
required alcohol 54-57 (10 mmol) at 0 °C under nitrogen was added
dropwise thionyl chloride (285.5 mg, 2.4 mmol). The reaction
mixture was allowed to reflux overnight then cooled to room
temperature and the solvent was removed to give the desired
products 58-69.
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obtained (575.2 mg, 78% yield) as a white solid (mp: 143 C). IR
spectrum (film), cm-1: 2974, 2936, 1724 (C=O), 1612, 1505, 1447,
1322, 1243, 1160. 1H NMR (300 MHz, CDCl3) δ ppm: 1.38 (6H, s, 2 x
CH3), 1.77 (2H, t, J = 6.6 Hz, C-3'H), 2.73 (2H, t, J = 6.6 Hz, C-4'H), 3.80
& 3.83 (6H, 2s, 2 x OCH3), 6.35 (1H, s, C-8'H), 6.44 (1H, d, J = 15.9 Hz,
C-2H), 7.26 (1H, s, C-5'H), 6.90 (2H, d, J = 8.4 Hz, C-3'' & C-5''), 7.07
(E)-Methyl 3-(7'- methoxy-2', 2'-dimethylchroman-6'-yl)
acrylate (58). Following the general procedure, with carboxylic acid
51 (524.6 mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol) and
methanol 54 (320 mg, 10 mmol), (E)-methyl 3-(7'- methoxy-2',2'-
dimethylchroman-6'-yl)acrylate (58) was obtained (425.2 mg, 77%
(2H, d, J = 8.4 Hz, C-2''H & C-6''H), 8.29 (1H, d, J =15.9 Hz, C-3H). 13
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NMR (75.5 MHZ, CDCl3) δ ppm: 21.51 (C-4'), 26.88 (2 x CH3), 32.76 (C-
3'), 55.47 & 55.57 (2 x OCH3), 75.36 (C-2'), 100.15 (C-8'), 113.20 (C-
10'), 114.37 (C-2), 114.47 (C-3'' & C-5''), 115.62 (C-6'), 122.50 (C-2''&
C-6''), 130.85 (C-5'), 142.13 (C-3), 144.58 (C-1''), 157.00 (C-4''), 157.50
(C-9'), 158.63 (C-7'), 166.82 (C=O). HRMS: found 369.1697 [M+H]+;
calculated 369.1697 for C22H25O5.
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yield) as a white solid (mp: 104 C). IR spectrum (KBr), cm-1: 2965,
2932, 1722 (C=O), 1611, 1491, 1322, 1201. 1H NMR (300 MHz, CDCl3)
δ ppm: 1.34 (6H, s, 2 x CH3), 1.79 (2H, t, J = 6.6 Hz, C-3'H), 2.71 (2H, t,
J = 6.6 Hz, C-4'H) , 3.77 (3H, s, C-1''H), 3.81 (3H, s, OCH3), 6.32 (1H, s,
C-8'H), 6.40 (1H, d, J =15.9 Hz, C-2H), 7.20 (1H, s, C-5'H), 7.88 (1H, d,
J = 15.9 Hz, C-3H). 13C NMR (75.5 MHZ, CDCl3) δ ppm: 21.55 (C-4'),
26.89 (2 x CH3), 32.82 (C-3'), 51.39 (OCH3), 55.47 (C-1''), 75.25 (C-2'),
100.15 (C-8'), 113.11 (C-10'), 115.07 (C-2), 115.78 (C-6'), 130.36 (C-
5'), 140.49 (C-3), 157.16 (C-9'), 158.40 (C-7'), 168.46 (C=O). HRMS:
found 277.1431 [M+H]+; calculated 277.1434 for C16H21O4.
(E)-Methyl 3-(7',8'-dimethoxy-2', 2'-dimethylchroman-6'-yl)
acrylate (62). Following the general procedure, with carboxylic acid
52 (584.6 mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol) and
methanol 54 (320 mg, 10 mmol), (E)-methyl 3-(7',8'-dimethoxy-2', 2'-
dimethylchroman-6'-yl) acrylate (62) was obtained (496.1 mg, 81%
yield) as a viscous oil. IR spectrum (film), cm-1: 2975, 2933, 1715
(C=O), 1628, 1568, 1464, 1320, 1254, 1166. 1H NMR (300 MHz, CDCl3)
δ ppm: 1.39 (6H, s, 2 x CH3), 1.82 (2H, t, J = 6.6 Hz, C-3'H), 2.75 (2H, t,
J = 6.6 Hz, C-4'H) , 3.78 (3H, s, C-1''H), 3.89 (6H, s, 2 x OCH3), 6.38 (1H,
d, J = 15.9 Hz, C-2H), 7.02 (1H, s, C-5'H), 7.87 (1H, d, J = 15.9 Hz, C-
3H). 13C NMR (75.5 MHZ, CDCl3) δ ppm: 22.12 (C-4'), 26.89 (2 x CH3),
32.51 (C-3'), 51.51 (C-1''), 60.69 & 61.53 (2 x OCH3), 75.38 (C-2'),
115.81 (C-2), 117.85 (C-6'), 119.53 (C-10'), 123.00 (C-5'), 140.09 (C-
3), 141.81 (C-8'), 150.37 (C-9'), 151.49 (C-7'), 168.12 (C=O). HRMS:
found, m/z: 307.1689 [M+H]+; calculated m/z: 307.1697 for C17H23O5.
(E)-Ethyl 3-(7'-methoxy-2', 2'-dimethylchroman-6'-yl) acrylate
(59). Following the general procedure, with carboxylic acid 51 (524.6
mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol) and ethanol 55
(460 mg, 10 mmol), (E)-ethyl 3-(7'-methoxy-2', 2'-dimethylchroman-
6'-yl) acrylate (59) was obtained (464.2 mg, 80% yield) as a viscous
oil. IR spectrum (film), cm-1: 2976, 2936, 1706 (C=O), 1613, 1491,
1448, 1320, 1257, 1160. 1H NMR (300 MHz, CDCl3) δ ppm: 1.29 (3H,
t, J = 7.2 Hz, C-2''H), 1.32 (6H, s, 2 x CH3), 1.79 (2H, t, J = 6.6 Hz, C-
3'H), 2.70 (2H, t, J = 6.6 Hz, C-4'H), 3.81 (3H, s, OCH3), 4.23 (2H, q, J =
7.2 Hz, C-1''H), 6.33 (1H, s, C-8'H), 6.40 (1H, d, J = 15.9 Hz, C-2H), 7.20
(1H, s, C-5'H), 7.88 (1H, d, J = 15.9 Hz, C-3H). 13C NMR (75.5 MHZ,
CDCl3) δ ppm: 14.41 (C-2''), 21.53 (C-4'), 26.87 (2 x CH3), 32.81 (C-3'),
55.49 (C-1''), 59.86 (OCH3), 74.78 (C-2'), 100.12 (C-8'), 101.60 (C-10'),
110.13 (C-6'), 113.06 (C-5'), 127.79 (C-2), 138.47 (C-3), 154.11 (C-9'),
157.07 (C-7') and 168.03 (C=O). HRMS: found 291.1594 [M+H]+;
calculated 291.1591 for C17H23O4.
(E)-Ethyl 3-(7',8'-dimethoxy-2', 2'-dimethylchroman-6'-yl)
acrylate (63). Following the general procedure, with carboxylic acid
52 (584.6 mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol) and
ethanol 55 (460 mg, 10 mmol), (E)-ethyl 3-(7',8'-dimethoxy-2', 2'-
dimethylchroman-6'-yl) acrylate (63) was obtained (505.5 mg, 79%
yield) as a viscous oil. IR spectrum (film), cm-1: 2975, 2932, 1714
(C=O), 1628, 1568, 1466, 1350, 1254, 1166. 1H NMR (300 MHz, CDCl3)
δ ppm: 1.32 (3H, t, J = 7.2 Hz, C-2''H), 1.39 (6H, s, 2 x CH3), 1.81 (2H,
t, J = 6.6 Hz, C-3'H), 2.75 (2H, t, J = 6.6 Hz, C-4'H), 3.89 (6H, s, 2 x
OCH3), 4.23 (2H, q, J = 7.2 Hz, C-1''H), , 6.37 (1H, d, J = 15.9 Hz, C-2H),
(E)-Phenyl 3-(7'-methoxy-2', 2'-dimethylchroman-6'-yl) acrylate
(60). Following the general procedure, with carboxylic acid 51 (524.6
mg, 2.0 mmol), thionyl chloride (285.5 mg, 2.4 mmol) and phenol 56
(941.1 mg, 10 mmol), (E)-phenyl 3-(7'-methoxy-2', 2'-
10 | J. Name., 2012, 00, 1-3
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