1
862
Can. J. Chem. Vol. 79, 2001
tered. Removal of the organic solvents on the rotary evapo-
rator yielded an orange-brown oil, which was purified by
silica gel column chromatography using 1:1 hexane:dichloro-
methane as eluant to yield a yellow oil (2.73 g, 0.008 mol,
6-[2-(Phenyl)ethoxy]-1-indanone (6c)
To an oven-dried 100-mL round-bottom flask equipped
with magnetic stirrer, reflux condenser, and nitrogen inlet
was added freshly distilled acetone (50 mL), 1-tosyloxy-2-
phenylethane (0.50 g, 0.0018 mol), anhydrous potassium
carbonate (0.28 g, 0.002 mol), and 6-hydroxy-1-indanone
(0.24 g, 0.0016 mol). The mixture was then refluxed under
nitrogen for 48 h. The dark brown mixture was stripped of
solvent to leave a grey-brown residue, which was acidified
by the addition of 0.4 M H SO (20 mL) and concd HCl
6
5%). The compound was identified as 5b on the basis of
the following data. MS (m/e) (I): 332(10), 135(100), 120(7),
05(56), 91(28), 77(68), 65(12), 51(16). HRMS calcd. for
C H O : 332.1413; found: 332.1413. UV ꢂ (MeCN)
1
2
2
20
3
max
–
1
–1
(
(
(
(
2
6
7
7
1
1
1
7
nm): 220 nm) (ꢄ 28 300 M cm ), sh. 252, 305. IR
KBr, cm ): 3060 (w), 2939 (w), 2835 (w), 1658 (m), 1596
–
1
2
4
m), 1488 (m), 1438 (m), 1281 (s), 1164 (m), 1043 (s), 971
(1 mL), and then extracted with a mixture of ether (50 mL)
and benzene (5 mL). The resulting bright yellow organic
phase was washed with 10% aq NaOH (30 mL), water
(30 mL), and brine (30 mL), and then dried with anhydrous
magnesium sulfate. The solvent was removed under reduced
pressure to yield an orange semisolid (0.44 g), which was
recrystallized from methanol to yield yellow needles (mp
69.0–71°C; 0.26 g, 0.001 mol, 64%). The compound was
identified as 6c on the basis of the following data. MS (m/e)
(I): 252 (10), 105 (100), 91 (13), 79 (20), 77 (23), 65 (7), 51
1
w), 872 (w), 781 (s), 724 (s). H NMR (CDCl ) d: 3.07 (t,
3
H, J = 7 Hz), 3.77 (s, 3H), 4.20 (t, 2H, J = 7 Hz), 6.75–
.86 (m, 3H), 7.08–7.12 (m, 1H), 7.20 (d, 1H, J = 8 Hz),
.31–7.35 (m, 3H), 7.42–7.47 (m, 2H), 7.53–7.58 (m, 1H),
.76–7.79 (m, 2H). 13C NMR (CDCl ) d: 35.6, 55.0, 68.6,
3
11.7, 114.7, 115.0, 119.2, 121.2, 122.7, 128.1, 129.1,
29.4, 129.9, 132.3, 137.7, 138.7, 139.5, 158.6, 159.6,
96.3. Anal. calcd. for C H O : C 79.50, H 6.06; found: C
2
0
22
3
9.90, H 5.93.
(
2
2
10). HRMS calcd. for C H O : 252.115028; found:
17 16 2
–
1
–1
52.115080. UV ꢂ
(MeCN): 205 (ꢄ 24 555 M cm ),
max
6
-[2-(3-Methoxyphenyl)ethoxy]-1-indanone (6b)
–
1
–1
–1
–1
13 (ꢄ 24 691 M cm ), 244 (ꢄ 8200 M cm ), 316
To a 25 mL round-bottom flask fitted with a condenser,
–1
–1
–1
(
ꢄ 3600 M cm ). IR (KBr, cm ): 3061 (vw), 2948 (w),
nitrogen inlet, and magnetic stirrer was added anhydrous
potassium carbonate (0.47 g, 0.0034 mol), acetone
918 (w), 1705 (vs), 1620 (w), 1491, 1447, 1297, 1254,
226, 1196 (w), 1170 (w), 1018, 918 (vw), 835, 720, 696.
(
1
10 mL), 6-hydroxy-1-indanone (0.46 g, 0.0034 mol), and
-bromo-2-(3-methoxyphenyl)ethane (1.51 g, 0.007 mol).
The mixture was refluxed under a nitrogen atmosphere for
0 days, with periodic monitoring by TLC. Additional
quantities of acetone (10 mL) and potassium carbonate
0.50 g) were added, and the mixture was then refluxed for
3
13
H), 4.15 (t, 2H, J = 7 Hz), 7.09–7.32 (m, 8H). C NMR
3
1
27.5, 128.7, 129.1, 138.2, 138.4, 148.1, 158.7, 207.0. Anal.
1
7
16
2
(
.59.
a further 5 days. The mixture was filtered and the solvent
was removed on the rotary evaporator to yield a red oil,
which was taken up in ether (50 mL) and 2% aq HCl
-[2-(Phenyl)ethoxy]-1-indanone (7)
This compound was prepared in analogous fashion to
(
50 mL). The layers were separated, and the aqueous frac-
tion was extracted with ether (2 × 50 mL). The organic
fractions were combined, washed with water (100 mL) and
brine (100 mL), dried with anhydrous magnesium sulfate,
and filtered. Removal of the ether under reduced pressure
yielded an orange oil (1.4 g), which was purified by col-
umn chromatography using 10% ethyl acetate in hexanes as
eluant, followed immediately by column chromatography
using chloroform as an eluant. The product was obtained as
a yellow oil (0.47 g, 0.0016 mol, 53%), which was identi-
6c, from 1-tosyloxy-2-phenylethane (1.16 g, 0.0042 mol),
5-hydroxy-1-indanone (0.61 g, 0.0041 mol), and anhydrous
potassium carbonate (0.70 g, 0.005 mol) in dry acetone
(50 mL). After refluxing under nitrogen for 5 days, the
reaction mixture was worked up as above to yield an or-
ange solid (1.09 g), which was recrystallized from metha-
nol to yield a pale yellow powder (mp 79 to 79.5°C; 0.48 g,
0.0019 mol, 46%). The compound was identified as 7 on
1
the basis of the following data. H NMR (CDCl3) d: 2.59 (t,
1
fied as 6b on the basis of the following data. H NMR
2H, J = 6 Hz), 2.99 (t, 2H, J = 6 Hz), 3.06 (t, 2H, J =
7 Hz), 4.18 (t, 2H, J = 7 Hz), 6.83 (d, 2H, J = 6 Hz), 7.18–
(
(
7
1
1
1
2
CDCl ) d: 2.61 (m, 2H), 3.00 (m, 4H), 3.71 (s, 3H), 4.12
t, J = 7 Hz, 2H), 6.65–6.72 (m, 1H), 6.8 (m, 2H), 7.08–
3
1
3
7.27 (m, 5H), 7.61 (d, 1H, J = 9 Hz). C NMR (CDCl3) d:
26.0, 35.7, 36.5, 69.2, 110.6, 115.7, 125.5, 126.8, 128.7,
129.1, 130.6, 137.9, 158.1, 164.6, 205.2. UV ꢂmax (MeCN):
.2 (m, 3H), 7.22 (d, J = 8 Hz, 1H), 7.74 (d, J = 3 Hz,
1
3
H). C NMR (CDCl ) d: 25.1, 35.6, 37.0, 68.9, 105.9,
3
–
1
–1
–1
–1
11.9, 114.8, 121.3, 124.3, 127.4, 128.3, 129.5, 138.2,
200 (ꢄ 24 500 M cm ), 220 (ꢄ 17 000 M cm ), 264 (ꢄ
–
1
–1
–1
–1
39.6, 148.0, 158.6, 159.8, 206.9. UV ꢂ
(MeCN) (nm):
17 800 M cm ), 287 (ꢄ 10 000 M cm ), 295 (ꢄ
max
–
1
–1
–1
–1
–1
18 (ꢄ 29 250 M cm ), sh. 243, 272, 279, 315. IR
10 000 M cm ). IR (KBr, cm ): 3060 (vw), 3039 (vw),
2938 (w), 2908(w), 1702 (vs), 1593 (s), 1489, 1460, 1440,
1303, 1255 (vs), 1140, 1089, 1013, 855, 835, 806, 760, 708,
643 (w), 588, 535 (vw). MS (m/e) (I): 252 (17), 105 (100),
91 (15), 79 (25), 77 (33), 65 (11), 51 (13). HRMS calcd. for
C17H16O2: 252.115028; found: 252.110220. Anal. calcd. for
C17H16O2: C 80.93, H 6.39; found: C 81.09, H 6.52.
–
1
(
(
KBr, cm ): 3005 (w), 2925 (w), 2837 (w), 1711 (s), 1613
w), 1492 (m), 1446 (w), 1296 (m), 1275 (m), 1222 (m),
1
5
168 (w), 1155 (w), 1040 (m), 837 (w), 785 (w), 697 (w),
58 (w), 530 (w). MS (m/e) (I): 282 (18), 135 (100), 120
(
8), 105 (25), 91 (30), 67 (27), 65 (22), 51 (12), 43 (33).
HRMS calcd. for C H O : 282.1256; found: 282.1256.
1
8
18
3
Anal. calcd. for C H O : C 76.57, H 6.43; found: C
Nanosecond laser flash photolysis experiments employed
the pulses from a Lumonics TE-861M excimer laser filled
1
8
18
3
7
6.74, H 6.61.
©
2001 NRC Canada