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none (2 mmol) in ethylene dichloride (10 mL) at room
temperature. The reaction mixture was stirred at room
temperature or refluxed and, after completion of the
reaction (monitored by TLC), the mixture was cooled
and poured onto a solution of 6 N HCl (40 mL). Lastly,
the mixture was extracted with Cl2CH2 (20 mL) and the
organic extract was washed with water (15 mL), dried
over anhydrous Na2SO4, and evaporated in vacuo to
yield the crude product.
5.5.2. 1-(7-Bromo-4,6-dimethylindan-5-yl)-2-chloroethan-
1-ol (10). Yield: 43%; colorless oil, purified by pTLC
using hexane–ethanol (9:1) as eluent. 1H NMR: d
2.05–2.11 (m, 2H, CH2), 2.32 (s, 3H, CH3), 2.65 (br s,
1H, OH, ex), 2.55 (s, 3H, CH3), 2.96–3.02 (m, 4H,
2· CH2), 3.65 (dd, J = 3.8 Hz, J = 11.4 Hz, 1H, HCH),
3.98 (dd, J = 10.3 Hz, J = 11.4 Hz, 1H, HCH), 5.34–
5.41 (m, 1H, CH). Anal. Calcd for C13H16BrClO: C,
51.43; H, 5.31. Found: C, 51.47; H, 5.33.
5.4.1. 4-Bromo-5,7-dimethylindane (4)20. Yield: 78%;
white solid, mp: 32–34 ꢁC, purified by pTLC using hex-
5.5.3. 2-(7-Bromo-4,6-dimethylindan-5-yl)oxirane (11).
Yield: 42%; white solid, mp: 81–82 ꢁC, purified by pTLC
1
1
ane–ethyl acetate (9:1) as eluent. H NMR: d 2.11 (m,
using hexane–ethanol (8:2) as eluent. H NMR: d 2.10
J = 7.6 Hz, 2H, CH2), 2.19 (s, 3H, CH3), 2.36 (s, 3H,
CH3), 2.93 (t, J = 7.6 Hz, 2H, CH2), 2.98 (t,
J = 7.6 Hz, 2H, CH2), 6.87 (s, 1H, ar). 13C NMR: d
19.0, 22.8, 24.3, 32.9, 35.8, 119.7, 130.1, 132.7, 135.6,
142.2, 144.8. Anal. Calcd for C11H13Br: C, 58.69; H,
5.82. Found: C, 58.75; H, 5.84.
(m, J = 7.5 Hz, 2H, CH2), 2.30 (s, 3H, CH3), 2.48 (s,
3H, CH3), 2.74 (dd, J = 3.0 Hz, J = 5.6 Hz, 1H, HCH),
2.95–3.01 (m, 4H, 2· CH2), 3.24 (dd, J = 4.0 Hz,
J = 5.6 Hz, 1H, HCH), 3.96 (m, 1H). Anal. Calcd for
C13H15BrO: C, 58.44; H, 5.66. Found: C, 58.39; H, 5.65.
5.5.4. 2-(7-Bromo-2,2,4,6-dimethylindan-5-yl)ethan-1-ol
(15). Yield: 42%; white solid, mp: 74–76 ꢁC, purified
by pTLC using hexane–ethyl acetate (7:3) as eluent.
1H NMR: d 1.15 (s, 6H, 2· CH3), 1.39 (br s, 1H, OH,
ex) 2.17 (s, 3H, CH3), 2.42 (s, 3H, CH3), 2.76 (s, 2H,
CH2), 2.78 (s, 2H, CH2), 3.00 (t, J = 7.5 Hz, 2H, CH2),
3.71 (m, 2H, CH2). 13C NMR: d 16.7, 20.1, 29.8, 34.3,
38.5, 48.9, 51.0, 62.3, 121.6, 132.4, 134.2, 134.5, 141.8,
142.3. Anal. Calcd for C15H21BrO: C, 60.61; H, 7.12.
Found: C, 60.57; H, 7.10.
5.4.2. 7-Bromo-5-(2-iodoethyl)-4,6-dimethylindane (8).
Yield: 28%; white solid, mp: 80–81 ꢁC, purified by pTLC
1
using hexane–ethyl acetate (9:1) as eluent. H NMR: d
2.05 (m, J = 7.6, 2H, CH2), 2.17 (s, 3H, CH3), 2.39 (s,
3H, CH3), 2.92–2.97 (m, 4H, 2· CH2), 3.07–3.11 (m,
2H, CH2), 3.25–3.29 (m, 2H, CH2). 13C NMR: d 1.9,
16.6, 19.9, 23.8, 33.9, 36.4, 36.6, 121.6, 131.2, 133.6,
137.9, 142.9, 143.6. Anal. Calcd for C13H16BrI: C,
41.19; H, 4.25. Found: C, 41.14; H, 4.25.
5.4.3. 4-Bromo-2,2,5,7-tetramethylindane (13). Yield:
88%; colorless oil, purified by pTLC using hexane–ethyl
acetate (9:1) as eluent. 1H NMR: d 1.20 (s, 6H, 2· CH3),
2.16 (s, 3H, CH3), 2.36 (s, 3H, CH3), 2.75 (s, 2H, CH2),
2.81 (s, 2H, CH2), 6.87 (s, 1H, ar). 13C NMR: d 18.9,
22.8, 29.8, 39.3, 47.8, 50.4, 119.9, 130.1, 133.0, 135.6,
141.4, 144.0. Anal. Calcd for C13H17Br: C, 61.67; H,
6.77. Found: C, 61.72; H, 6.79.
5.6. General procedure for the preparation of 7 and 16
The correspondent alcohol (0.6 mmol) in dry THF
(3 mL) was added to a suspension of LiAlH4 (5 mmol)
in dry THF (15 mL) at 0 ꢁC. The reaction mixture was
heated under reflux during 24 h. After being cooled at
room temperature, the mixture was carefully poured
onto ice and a solution of 10% NaOH (5 mL) was add-
ed. The aqueous phase was extracted with Cl2CH2
(2· 10 mL). The extract was washed with water
(10 mL) dried over anhydrous Na2SO4 and evaporated
in vacuo to yield the crude product.
5.5. General procedure for the preparation of 6, 10, 11,
and 15
NaBH4 (12 mmol) was added over a period of 5 min to a
refluxing solution of the correspondent a-chloroketone
(1 mmol) in ethanol (18 mL). The reaction mixture was
heated under reflux until TLC showed the presence of
the desired product. The mixture was cooled at room
temperature and the solvent was removed in vacuo.
The residue was partitioned between CHCl3 (20 mL)
and water (10 mL). The organic layer was dried over
anhydrous Na2SO4, and evaporated in vacuo to yield
the crude product.
5.6.1. 2-(4,6-Dimethylindan-5-yl)ethan-1-ol (7). Yield:
67%; white solid, mp: 53–55 ꢁC, purified by pTLC using
hexane–ethyl acetate (8:2) as eluent. 1H NMR: d 1.42 (br
s, 1H, OH, ex), 2.07 (m, J = 7.6 Hz, 2H, CH2), 2.29 (s,
3H, CH3), 2.35 (s, 3H, CH3), 2.85 (t, J = 7.6 Hz, 2H,
CH2), 2.90 (t, J = 7.6 Hz, 2H, CH2), 2.99 (t,
J = 7.6 Hz, 2H, CH2), 3.77 (t, J = 7.6 Hz, 2H, CH2),
6.95 (s, 1H, ar). 13C NMR: d 16.6, 20.8, 25.2, 32.5,
33.2, 33.4, 62.4, 124.3, 132.3, 133.1, 135.3, 141.8,
142.3. Anal. Calcd for C13H18O: C, 82.06; H, 9.54.
Found: C, 82.11; H, 9.52.
5.5.1. 2-(7-Bromo-4,6-dimethylindan-5-yl)ethan-1-ol (6).
Yield: 41%; white solid, mp: 100–101 ꢁC, purified by
pTLC using hexane–ethyl acetate (7:3) as eluent. 1H
NMR: d 1.46 (br s, 1H, OH, ex), 2.08 (m, J = 7.6 Hz,
2H, CH2), 2.24 (s, 3H, CH3), 2.46 (s, 3H, CH3), 2.98
(m, 4H, 2· CH2), 3.04 (t, J = 7.4 Hz, 2H, CH2), 3.77
(t, J = 7.4 Hz, 2H, CH2). 13C NMR: d 16.8, 20.1, 23.8,
34.0, 34.3, 36.4, 62.3, 121.4, 132.1, 134.3, 134.5, 142.6,
143.1. Anal. Calcd for C13H17BrO: C, 58.01; H, 6.37.
Found: C, 57.98; H, 6.39.
5.6.2. 2-(2,2,4,6-Tetramethylindan-5-yl)ethan-1-ol (16)7.
Yield: 69%; white solid, mp: 65–67 ꢁC, purified by pTLC
1
using hexane–ethyl acetate (8:2) as eluent. H NMR: d
1.14 (s, 6H, 2· CH3), 1.43 (br s, 1H, OH, ex) 2.21 (s,
3H, CH3), 2.32 (s, 3H, CH3), 2.65 (s, 2H, CH2), 2.69
(s, 2H, CH2), 2.94 (t, J = 7.4 Hz, 2H, CH2), 3.73 (m,
2H, CH2), 6.85 (s, 1H, ar). 13C NMR: d 16.5, 20.8,
29.7, 33.2, 39.6, 47.6, 48.3, 62.4, 124.6, 132.3, 133.3,