5308 Kilaru et al.
Asian J. Chem.
1
cation. H and 13C NMR spectra were recorded on a Bruker
6.92 (d, 1H, J = 8.1 Hz), 7.53-7.58 (m, 1H), 7.53-7.58 (m,
1H); 13C NMR (75 MHz, CDCl3) δ 25.82, 31.71, 45.08, 55.60,
65.11, 110.26, 111.23, 122.80, 130.36, 148.98, 152.20, 196.25;
MS(ESI, m/z): 225 [M + H]+, 247 [M + Na]+.Anal. calcd. (%)
for C12H16O4 (224.25): C, 64.27; H, 7.19; found (%): C, 64.13;
H, 7.10.
Avance 300 and 75 MHz spectrometer, respectively. 1H NMR
spectra were reported using Me4Si (δ 0.0 ppm) as internal
standard. 13C NMR were reported relative to CDCl3 (δ 77.16
ppm) and DMSO-d6 (δ 48.5 ppm). FTIR spectra were recorded
on a Perkin-Elmer Spectrum one spectrometer by using 1 %
potassium bromide pellet technique and are reported in wave
numbers (cm-1). LC mass spectra were recorded on Agilent
1100 series LC-MSD-TRAP-SL system mass spectrometer.
All the solvents and reagents were used without further purifi-
cation.
Synthesis of 1-[4-(3-bromopropoxy)-3-methoxyphenyl]
ethanone (9): To a stirred solution of 1-(4-hydroxy-3-
methoxyphenyl)ethanone 2 (10 g, 60 mmol), acetonitrile
(50 mL), potassium carbonate (8.3 g, 60 mmol) and 1,3-
dibromopropane 8 (8.3 g, 60 mmol) were charged at room
temperature. Reaction temperature was raised to 80-85 ºC and
maintained for 8 h. The reaction progress was monitored by
TLC (n-hexane:ethyl acetate, 7:3), after completion of reaction,
the reaction mixture was cooled to room temperature, filtered
the salts and washed with acetonitrile (10 mL). Filtrate was
taken, solvent was removed under reduced pressure below
60 ºC, light brown coloured residue was obtained, it was
purified from column chromatography 10 % ethyl acetate in
n-hexane and recrystallized from isopropyl ether (50 mL),to
get a light brown coloured solid 9 (15.56 g, 90 %). Purity 99.2
% (by HPLC), m.p. 64-66 ºC; FT-IR (KBr, νmax, cm-1): 3073,
3008, 2958, 2932, 2841, 1669, 1595, 1586, 1521, 1466, 1448,
1419, 1383, 1350, 1274, 1224, 1182, 1145, 1039, 1022, 873,
807; 1H NMR (300 MHz, CDCl3) δ 2.36-2.45 (m, 2H), 2.57
(s, 3H), 3.63 (t, 2H, J = 6.3 Hz), 3.91 (s, 3H), 4.23 (t, 2H, J =
5.9 Hz), 6.92 (d, 1H, J = 8.4 Hz), 7.53-7.58 (m, 1H), 7.53-
7.58 (m, 1H); 13C NMR (75 MHz, CDCl3) δ 26.08, 29.70,
31.99, 55.88, 66.38, 110.50, 111.46, 123.03, 130.65, 149.23,
152.39, 196.58; MS(ESI, m/z): 287 [M + H]+, 309 [M + Na]+.
Anal. calcd. (%) for C12H15O3Br (286.02): C, 50.19; H, 5.27;
found (%): C, 50.14; H, 5.22.
Synthesis of 1-[4-(3-chloropropoxy)-3-methoxyphenyl]
ethanone (4): To a stirred solution of 1-(4-hydroxy-3-
methoxyphenyl) ethanone 2 (5 g, 30 mmol), acetonitrile (20
mL) and potassium carbonate (12.5 g, 9 mmol) were charged
at room temperature. Reaction temperature was raised to 75-
80 ºC, 1-bromo-3-chloropropane 3 (8.35 g, 53 mmol) in
acetonitrile (20 mL) was added during 4 h dropwise at ambient
temperature and maintained for 3 h. The reaction progress
was monitored by TLC (methylene dichloride: methanol, 4:1)
after completion of reaction, it was cooled to room tempe-
rature and filtered the salts. Filtrate was taken and the solvent
was removed under reduced pressure below 60 ºC and recrys-
tallized from cyclohexane (30 mL) as a white crystalline solid
4 (6.93 g, 95 %) obtained. Purity 99.5 % (by HPLC), m.p. 61-
63 ºC; FT-IR (KBr, νmax, cm-1): 3072, 2964, 2933, 2842, 2878,
1670, 1596, 1587, 1523, 1515, 1466, 1452, 1420, 1355, 1277,
1225, 1183, 1146, 1077, 1034, 873, 806, 757, 722; 1H NMR
(300 MHz, CDCl3) δ 2.28-2.36 (m, 2H), 2.57 (s, 3H), 3.78 (t,
2H, J = 6.2 Hz), 3.91 (s, 3H), 4.24 (t, 2H, J = 6.0 Hz), 6.92 (d,
1H, J = 8.1 Hz), 7.53-7.58 (m, 1H), 7.53-7.58 (m, 1H); 13C
NMR (75 MHz, CDCl3) δ 25.82, 31.71, 41.08, 55.60, 65.11,
110.26, 111.23, 122.80, 130.36, 148.98, 152.20, 196.25; MS
(ESI, m/z): 243 [M + H]+, 265 [M + Na]+. Anal. calcd. (%) for
C12H15ClO3 (242.70): C, 59.39; H, 6.23; Found (%): C, 59.28;
H, 6.17.
Synthesis of 1,1'-(4, 4'-(propane-1,3-diylbis(oxy))bis(3-
methoxy-4, 1-phenylene)) diethanone (10): To a stirred
solution of 1-(4-hydroxy-3-methoxyphenyl) ethanone 2 (20
g, 120 mmol), acetonitrile (100 mL), potassium carbonate
(50.56 g, 361 mmol) and 1,3-dibromopropane 8 (72.9 g, 361
mmol) were charged at room temperature. Reaction tempe-
rature was raised to 80-85 ºC and maintained for 12 h. The
reaction progress was monitoring by TLC (n-hexane:ethyl
acetate, 7:3), after completion of reaction, it was cooled to
room temperature, filtered the salts and washed with acetoni-
trile (20 mL). Filtrate was taken and the solvent was removed
under reduced pressure below 60 ºC, light white coloured
residue was obtained, it was purified from column chroma-
tography 10 % ethyl acetate in n-hexane and recrystallized
from methylene dichloride:n-hexane (40:80 mL), as a white
coloured solid 10 (35.8 g, 80 %) was obtained. Purity 98.5 %
(by HPLC), m.p. 116-118 ºC; FT-IR (KBr, νmax, cm-1): 3081,
2958, 2938, 1671, 1586, 1513, 1462, 1450, 1417, 1345, 1273,
1220, 1147, 1050, 1031, 1022, 875, 807, 795; 1H NMR (300
MHz, CDCl3) δ 2.38-2.46 (m, 2H), 2.56 (s, 6H), 3.91 (s, 6H),
4.32 (t, 4H, J = 6.2 Hz), 6.94 (d, 2H, J = 8.1 Hz), 7.53-7.56
(m, 2H), 7.53-7.56 (m, 2H); 13C NMR (75 MHz, CDCl3) δ
26.05, 28.81, 55.84, 65.26, 110.36, 111.33, 123.04, 130.47,
149.15, 152.48, 196.61; MS(ESI, m/z): 373 [M + H]+, 395 [M
+ Na]+. Anal. calcd. (%) for C21H24O6 (372.16): C, 67.73; H,
6.50; found (%): C, 50.09; H, 5.19.
Synthesis of 1-[4-(3-hydroxypropoxy)-3-methoxy-
phenyl]ethanone (7): To a stirred solution of 1-(4-hydroxy-
3-methoxyphenyl)ethanone 2 (5 g, 30 mmol), N,N-dimethyl
formamide (25 mL) and potassium carbonate (12.5 g, 9 mmol)
were charged at room temperature. Reaction temperature was
raised to 70-75 ºC, 3-chloropropan-1-ol 6 (3.2 g, 33 mmol)
was added drop wise at ambient temperature.After maintaining
at 70-75 ºC for 3 h, progress of the reaction was monitored by
TLC (methylene dichloride: methanol, 4:1) reaction mixture
was cooled to room temperature. Reaction mass was quenched
into water (50 mL) and ethyl acetate (100 mL), further pH
was adjusted to 6.5 by using acetic acid (10 mL). Two layers,
were separated, organic layer was washed with water twice
(50 mL × 2 mL) and washed with 10 % sodium chloride (50
mL). Organic layer was taken and ethyl acetate was completely
distilled off an oily residue was obtained, it was recrystallized
from isopropyl ether (50 mL), light pink coloured solid 7 (6.47
g, 96 %) was obtained. Purity 99.16 % (by HPLC), m.p. 79-
81 ºC; FT-IR (KBr, νmax, cm-1): 3011, 2955, 2923, 2842, 1663,
1590, 1552, 1501, 1470, 1422, 1349, 1262, 1211, 1175, 1143,
1075, 1043, 852, 806, 762, 721; 1H NMR (300 MHz, CDCl3)
δ 2.13-2.18 (m, 2H), 2.55 (s, 3H), 3.78 (t, 2H, J = 6.2 Hz),
3.91 (s, 3H), 4.25 (t, 2H, J = 6.0 Hz), 4.39 (t, 1H, J = 6.8 Hz),