514
M.R. Charan Raja et al. / European Journal of Medicinal Chemistry 139 (2017) 503e518
chromatography: 4% ethyl acetate in hexane. Yield: 76.1%;
Appearance: White semi-solid. H NMR (300 MHz) (CDCl ) e
3
4.2.2.18. 4-Nitro-benzoic acid 4-allyl-2-methoxy-phenyl ester (20).
Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP (0.007 g;
0.06 mmol), 4-nitrobenzoic acid (0.102 g; 0.6 mmol), DCC (0.151 g;
0.73 mmol). Solvent system for column chromatography: 4% ethyl
acetate and hexanes. Yield: 62.4%; Appearance: White solid; m.p:
1
d
(ppm) 0.88 (t, J ¼ 6.9 Hz, 3H), 1.25e1.46 (m, 26H), 1.82 (quintet,
J ¼ 7.2 Hz, 2H), 3.33 (d, J ¼ 6.9 Hz, 2H), 3.85 (s, 3H), 3.98 (t,
J ¼ 6.9 Hz, 2H), 5.04e5.11 (m, 2H), 5.89e6.03 (m, 1H), 6.69e6.82 (m,
1
3
ꢀ
1
3
Ar-H). C NMR (75 MHz) (CDCl
3
) e
d
(ppm) 14.1, 22.7, 26.0, 29.2,
82e84 C. H NMR (300 MHz) (CDCl
3
) e
d
(ppm) 3.42 (d, J ¼ 6.6 Hz,
2
9.4, 29.4, 29.6, 29.6, 29.7, 29.7, 31.9, 39.8, 56.0, 69.2, 112.4, 113.1,
2H), 3.81 (s, 3H), 5.10 (t, J ¼ 1.2 Hz, 1H), 5.14e5.17 (m, 1H),
1
C
15.6, 120.4, 132.6, 137.8, 146.9, 149.4. HRMS (ESIþ): m/z calcd for
5.92e6.06 (m,1H), 6.83 (d, J ¼ 2.1 Hz,1Ar-H), 6.85 (s,1Ar-H), 7.07 (d,
þ
13
H
26 45
O
2
[MþH] : 389.3420; found: 389.3426.
J ¼ 7.8 Hz, 1Ar-H), 8.33e8.41 (m, 4Ar-H). C NMR (75 MHz) (CDCl
3
)
e
d (ppm) 40.1, 55.9, 112.9, 116.3, 120.8, 122.3, 123.6, 131.4, 135.0,
1
C
36.9, 137.7, 139.7, 150.7, 150.8, 163.0. HRMS (ESIþ): m/z calcd for
4
.2.2.14. 4-Allyl-2-methoxy-1-octadec-9-enyloxy-benzene
Method B: Amount of eugenol (0.086 g, 0.523 mmol), Oleyl chloride
0.3 g, 1.045 mmol), K CO (0.289 g, 2.092 mmol). Solvent system
for column chromatography: 4% ethyl acetate in hexane. Yield:
(16).
þ
17
H16NO
5
[MþH] : 314.1028; found: 314.1030.
(
2
3
4
.2.2.19. 3-Nitro-benzoic acid 4-allyl-2-methoxy-phenyl ester (21).
Method C2: Amount of Eugenol (0.094 g, 0.58 mmol), DMAP
0.007 g, 0.058 mmol), EDCI.HCl (0.144 g, 0.754 mmol), m-Nitro-
benzoic acid (0.107 g, 0.638 mmol) and THF (3 ml). Yield: 31.8%;
1
6
d
3
0.3%; Appearance: Colourless liquid. H NMR (300 MHz) (CDCl ) e
(
(ppm) 0.88 (t, J ¼ 6.9 Hz, 3H), 1.26e1.44 (m, 23H), 1.80e1.85 (m,
2
H), 1.98e2.02 (m, 3H), 3.33 (d, J ¼ 6.6 Hz, 2H), 3.85 (s, 3H), 3.98 (t,
1
Appearance: White semi-solid. H NMR (300 MHz) (CDCl
d
3
) e
(ppm) 3.42 (d, J ¼ 6.9 Hz, 2H), 3.81 (s, 3H), 5.11e5.17 (m, 2H),
.93e6.06 (m, 1H), 6.83e6.85 (m, 2H), 7.08 (d, J ¼ 7.8 Hz, 1H), 7.72
J ¼ 6.9 Hz, 2H), 5.04e5.12 (m, 2H), 5.35 (t, J ¼ Hz, 2H), 5.89e6.03 (m,
13
1
H), 6.68e6.82 (m, 3Ar-H). C NMR (75 MHz) (CDCl
3
) e d (ppm)
5
14.1, 22.7, 26.0, 27.2, 29.3, 29.3, 29.4, 29.5, 29.5, 29.7, 29.8, 29.8, 31.9,
13
(
t, J ¼ 8.1 Hz,1H), 8.47e8.55 (m, 2H), 9.05 (t, J ¼ 1.8 Hz,1H). C NMR
3
9.8, 56.0, 69.2, 112.4, 113.1, 115.6, 120.4, 129.8, 130.0, 132.6, 137.7,
(75 MHz) (CDCl ) e (ppm) 40.1, 55.8, 112.9, 116.3, 120.8, 122.4,
3
d
þ
1
46.9, 149.4. HRMS (ESIþ): m/z calcd for C28
H
47
O
2
[MþH] :
125.3,127.8, 129.8,131.1, 135.9,137.0, 137.7, 139.6,148.4, 150.8, 162.8.
415.3576: found: 415.3580.
þ
HRMS (ESIþ): m/z calcd for C17
H16NO
5
[MþH] : 314.1028; found:
314.1025.
4.2.2.15. Acetic
acid
4-allyl-2-methoxy-phenyl
ester
(17).
Method A2: Amount of Eugenol (0.1 g; 0.6 mmol), Pyridine
0.095 g; 1.2 mmol), acetic anhydride (0.075 g; 0.73 mmol). Solvent
4.2.2.20. 1H-indole-3-carboxylic acid 4-allyl-2-methoxy-phenyl ester
(22). Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP
(0.007 g; 0.06 mmol), indole-3-carboxylic acid (0.097 g; 0.6 mmol),
DCC (0.151 g; 0.73 mmol). Solvent system for column chromatog-
raphy: 22% ethyl acetate and hexanes. Yield: 74.6%; m.p:
(
system for column chromatography: 4% ethyl acetate and hexanes.
1
Yield: 67.5%; Appearance: colourless liquid. H NMR (300 MHz)
(
5
CDCl
3
) e
d
(ppm) 2.30 (s, 3H), 3.37 (d, J ¼ 6.6 Hz, 2H), 3.82 (s, 3H),
ꢀ
1
.07e5.13 (m, 2H), 5.89e6.02 (m, 1H), 6.75e6.79 (m, 2Ar-H), 6.96
168e170 C; Appearance: white solid. H NMR (300 MHz) (CDCl ) e
3
13
(
4
d, J ¼ 7.8 Hz, 1Ar-H). C NMR (75 MHz) (CDCl
3
) e
d
(ppm) 20.7,
d
(ppm) 3.41 (d, J ¼ 6.9 Hz, 2H), 3.81 (s, 3H), 5.09e5.10 (m, 1H),
0.1, 55.8, 112.7, 116.2, 120.7, 122.5, 137.1, 138.0, 139.0, 150.9, 169.3.
5.11e5.16 (m, 1H), 5.92e6.06 (m, 1H), 6.81 (d, J ¼ 1.8 Hz, 1Ar-H),
6.84 (s, 1Ar-H), 7.11 (d, J ¼ 8.1 Hz, 1Ar-H), 7.26e7.31 (m, 2Ar-H),
7.43e7.48 (m, 1Ar-H), 8.10 (d, J ¼ 3.0 Hz, 1Ar-H), 8.26 (q, J ¼ 3.0 Hz,
þ
HRMS (ESIþ): m/z calcd for C12
H
15
O
3
[MþH] : 207.1021; found:
2
07.1024.
13
1
6
Ar-H), 8.70 (bs, 1N-H). C NMR (75 MHz) (Acetone-d ) e d (ppm)
4
1.8, 57.3, 114.2, 114.9, 117.2, 122.3, 122.4, 123.0, 123.4, 123.6, 124.8,
4
.2.2.16. 4-Fluoro-benzoic acid 4-allyl-2-methoxy-phenyl ester (18).
1
25.3, 128.5, 134.8, 138.9, 139.7, 140.6, 153.9, 164.3. HRMS (ESIþ): m/
Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP (0.007 g;
0
0
þ
z calcd for C19
H18NO
3
[MþH] : 308.1287; found: 308.1291.
.06 mmol), 4-Fluorobenzoic acid (0.169 g; 0.6 mmol), DCC (0.151 g;
.73 mmol). Solvent system for column chromatography: 4% ethyl
4.2.2.21. Phenyl-acetic acid 4-allyl-2-methoxy-phenyl ester (23).
ꢀ
acetate and hexanes. Yield: 79.2%; m.p: 68e70 C; Appearance:
Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP (0.007 g;
0
0
white solid. 1H NMR (300 MHz) (CDCl
) e
d
(ppm) 3.41 (d,
3
.06 mmol), phenylacetic acid (0.082 g; 0.6 mmol), DCC (0.151 g;
.73 mmol). Solvent system for column chromatography: 4% ethyl
J ¼ 6.6 Hz, 2H), 3.81 (s, 3H), 5.08e5.11 (m, 1H), 5.12e5.17 (m, 1H),
5
.92e6.05 (m,1H), 6.80 (d, J ¼ 1.8 Hz,1Ar-H), 6.83 (s,1Ar-H), 7.06 (d,
acetate and hexanes. Yield: 89.2%; Appearance: colourless liquid.
13
J ¼ 7.8 Hz, 1Ar-H), 7.13e7.21 (m, 2Ar-H), 8.20e8.26 (m, 2Ar-H).
C
1
H NMR (300 MHz) (CDCl
3
) e
d
(ppm) 3.36 (d, J ¼ 6.6 Hz, 2H), 3.74
3
NMR (75 MHz) (CDCl ) e d (ppm) 40.1, 55.9, 112.8, 115.5, 115.8,
(
(
7
s, 3H), 3.88 (s, 2H), 5.06 (s, 1H), 5.10 (d, J ¼ 7.2 Hz, 1H), 5.90e6.01
m, 1H), 6.72 (s, 1Ar-H), 6.76 (s, 1Ar-H), 6.91 (d, J ¼ 7.8 Hz, 1Ar-H),
116.2,120.8,122.6,132.9, 133.0, 137.1, 138.1, 139.2, 151.0, 164.0,164.4,
þ
1
67.8. HRMS (ESIþ): m/z calcd for C17
H16FO
3
[MþH] : 287.1083;
13
.33 (m, 5Ar-H). C NMR (75 MHz) (CDCl
3
) e
d
(ppm) 40.1, 41.0,
found: 287.1081.
55.8, 112.8, 116.2, 120.7, 122.4, 127.1, 128.6, 128.8, 129.4, 129.5, 133.8,
1
37.1, 138.1, 139.0, 150.9, 169.8. HRMS (ESIþ): m/z calcd for C18
19 3
H O
þ
4
.2.2.17. 2-Chloro-benzoic acid 4-allyl-2-methoxy-phenyl ester (19).
Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP (0.007 g;
.06 mmol), 2-chlorobenzoic acid (0.094 g; 0.6 mmol), DCC
0.151 g; 0.73 mmol). Solvent system for column chromatography:
% ethyl acetate and hexanes. Yield: 81.0%; Appearance: colourless
[MþH] : 283.1334; found: 283.1332.
0
(
4
4.2.2.22. Phenoxy-acetic acid 4-allyl-2-methoxy-phenyl ester (24).
Method B2: Amount of Eugenol (0.1 g; 0.6 mmol), DMAP) (0.007 g;
0.06 mmol), phenoxyacetic acid (0.091 g; 0.6 mmol), DCC (0.151 g;
0.73 mmol). Solvent system for column chromatography: 4% ethyl
1
liquid. H NMR (300 MHz) (CDCl
3
) e
d
(ppm) 3.40 (d, J ¼ 6.9 Hz, 2H),
ꢀ
3
1
1
6
.83 (s, 3H), 5.07e5.10 (m, 1H), 5.11e5.16 (m, 1H), 5.91e6.05 (m,
acetate and hexanes. Yield: 93.2%; m.p: 55e57 C; Appearance:
1
H), 6.80 (d, J ¼ 1.8 Hz, 1Ar-H), 6.84 (s, 1Ar-H), 7.10 (d, J ¼ 8.1 Hz,
Ar-H), 7.35e7.40 (m,1Ar-H), 7.44e7.53 (m, 2Ar-H), 8.09 (dd, J ¼ 1.5,
white waxy solid. H NMR (300 MHz) (CDCl
3
) e
d
(ppm) 3.38 (d,
J ¼ 6.6 Hz, 2H), 3.80 (s, 3H), 4.90 (s, 2H), 5.07 (t, J ¼ 1.5 Hz, 1H),
.0 Hz, 1Ar-H). 13C NMR (75 MHz) (CDCl
) e d (ppm) 40.1, 55.9,
3
5.10e5.14 (m, 1H), 5.88e6.00 (m, 1H), 6.76 (d, J ¼ 1.8 Hz, 1Ar-H),
13
112.9, 116.2, 120.8, 122.6, 126.7, 129.3, 131.2, 132.1, 133.0, 134.4, 137.1,
6.79 (s, 1Ar-H), 6.96e7.04 (m, 4Ar-H), 7.30e7.36 (m, 2Ar-H).
C
1
38.0, 139.3, 151.0, 163.6. HRMS (ESIþ): m/z calcd for C17
H16 ClO
3
NMR (75 MHz) (CDCl
120.7, 121.8, 122.2, 129.5, 136.9, 137.3, 139.4, 150.6, 157.8, 167.2.
3
) e d (ppm) 40.0, 55.8, 65.2, 112.7, 114.8, 116.2,
þ
[MþH] : 303.0788; found: 303.0789.