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vacuo to yield white crystal of 1-bromo-3-ethyladamantane
(45.0 g, 185 mmol, 92%, bp 47–61 C/1.0 mmHg, mp 34–36
ꢀC). Ethyl group: C(b)H2C(a)H3.
with Et2O three times. The combined organic layer was dried
over anhydrous MgSO4 and filtered. After evaporation of
Et2O, the residue was distilled in vacuo to yield yellow liquid
of 1,3-dibromo-5-hexyladamantane (14.9 g, 39.4 mmol, 52%,
bp 170–180 ꢀC/0.70 mmHg). Hexyl group: C(f)H2C(e)H2C(d)
H2C(c)H2C(b)H2C(a)H3.
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1H NMR (300 MHz, CDCl3): d 0.77–0.82 (t, J 5 7.5 Hz, 3H,
C(a)H3), 1.13–1.20 (q, J 5 7.7 Hz, 2H, C(b)H2), 1.45–1.46 (2s,
4H, C(4)H2, C(10)H2), 1.57–1.72 (m, 2H, C(6)H2), 2.06 (s, 2H,
C(2)H2), 2.14 (bs, 2H, C(5)H, C(7)H), 2.22–2.33 (m, 4H,
C(8)H2, C(9)H2). 13C NMR (75 MHz, CDCl3): d 7.1 (Ca), 32.9
(C5, C7), 35.3 (C6), 35.8 (Cb), 38.1 (C3), 40.1 (C4, C10), 48.8
(C8, C9), 53.7 (C2), 67.3 (C1). IR (neat, cm21): 2903, 2848,
1455, 1304, 1356, 996, 955, 889, 820, 726, 676.
1H NMR (300 MHz, CDCl3): d 0.84–0.88 (t, J 5 6.1 Hz, 3H,
C(a)H3), 1.10–1.35 (m, 10H, C(b)H2, C(c)H2, C(d)H2, C(e)H2,
C(f)H2), 1.44 (bs, 2H, C(6)H2), 2.03 (bs, 4H, C(4)H2, C(9)H2),
2.19–2.24 (m, 5H, C(7)H, C(8)H2,C(10)H2), 2.72–2.81 (m, 2H,
C(2)H2). 13C NMR (75 MHz, CDCl3): d 14.2 (Ca), 22.6 and
22.7 (Cb, Cc), 30.0 (Cd), 31.9 (Ce), 34.8 (C7), 38.7 (C6), 41.6
(C5), 42.8 (Cf), 46.7 (C8, C10), 52.0 (C4, C9), 58.7 (C2), 62.5
(C1, C3). IR (neat, cm21): 2925, 2855, 1454, 1322, 1310,
1138, 1126, 957, 828, 705.
1-Bromo-3-isobutyladamantane
The reaction was performed following general procedure B,
starting from 1-isobutyladamantane (615 mg, 3.20 mmol) to
yield 1-bromo-3-isobutyladamantane as pale yellow oil (850
mg, 3.13 mmol, 98%). Isobutyl group: C(c)H2C(b)
H(C(a)H3)2.
1,3-Dibromo-5-octyladamantane
The reaction was performed following general procedure C,
starting from 1-octyladamantane (12.1 g, 48.7 mmol) to yield
1,3-dibromo-5-octyladamantane as pale orange oil (3.46 g,
8.52 mmol, 17%) after purification with column chromatog-
raphy (silica gel, hexane). Octyl group: C(h)H2C(g)H2C(f)H2
C(e)H2C(d)H2C(c)H2C(b)H2C(a)H3.
1H NMR (300 MHz, CDCl3): d 0.88–0.91 (d, J 5 6.7 Hz, 6H,
C(a)H3), 1.04–1.06 (d, J 5 5.3 Hz, 2H, C(c)H2), 1.50–1.51 (2s,
4H, C(4)H2, C(10)H2), 1.60–1.73 (m, 3H, C(b)H, C(6)H2), 2.11
(bs, 4H, C(2)H2, C(5)H, C(7)H), 2.22–2.35 (m, 4H, C(8)H2,
C(9)H2). 13C NMR (75 MHz, CDCl3): d 22.9 (Cb), 25.8 (Ca),
32.8 (C5, C7), 35.2 (C6), 41.1 (C4, C10), 48.9 (C8, C9), 53.0
(Cc), 54.6 (C2), 67.3 (C1). IR (neat, cm21): 2903, 2851,
1455, 1304, 1133, 974, 815, 735, 678.
1H NMR (300 MHz, CDCl3): d 0.86–0.90 (t, J 5 6.5 Hz, 3H,
C(a)H3), 1.10–1.33 (m, 14H, C(b)H2, C(c)H2, C(d)H2, C(e)H2,
C(f)H2, C(g)H2, C(h)H2) 1.46–1.47 (2s, 2H, C(6)H2), 2.05 (s,
4H, C(4)H2, C(9)H2), 2.18–2.30 (m, 5H, C(7)H, C(8)H2,
C(9)H2), 2.75–2.87 (m, 2H, C(2)H2). 13C NMR (75 MHz,
CDCl3): d 14.3 (Ca), 22.7 and 22.8 (Cb, Cc), 29.4, 29.7, and
30.4 (Cd, Ce, Cf), 32.0 (Cg), 34.9 (C7), 38.8 (C6), 41.7 (C5),
41.7 (Ch), 46.7 (C8, C10), 52.1 (C4, C9), 58.7 (C2), 62.6 (C1,
C3). IR (neat, cm21): 2925, 2853, 1455, 1322, 1310, 1138,
957, 829, 705.
1-Bromo-3-butyl-5-isobutyladamantane
The reaction was performed following general procedure B,
starting from 1-butyl-3-isobutyladamantane (11.0 g, 44.3
mmol) to yield 1-bromo-3-butyl-5-isobutyladamantane as
pale yellow oil (14.9 g, 45.5 mmol, 103%). Butyl and isobu-
tyl groups: C(d)H2C(c)H2C(b)H2C(a)H3, C(e)H2C(f)H(C(g)H3)2.
1H NMR (300 MHz, CDCl3): d 0.87–0.91 (m, 9H, C(a)H3,
C(g)H3), 1.06–1.08 (d, J 5 5.3 Hz, 2H, C(e)H2), 1.09–1.30 (m,
6H, C(b)H2, C(c)H2, C(d)H2), 1.33–1.50 (m, 4H, C(6)H2,
C(10)H2), 1.55 (s, 2H, C(4)H2), 1.63–1.73 (m, 1H, C(f)H),
2.00–2.26 (m, 7H, C(2)H2, C(7)H, C(8)H2, C(9)H2). 13C NMR
(75 MHz, CDCl3): d 14.3 (Ca), 23.0 (Cf), 23.7 (Cb), 25.0 (Cc),
25.8 (Cg), 32.8 (C7), 38.3 and 39.0 (C3, C5), 40.2 and 40.7
(C6, C10), 43.3 (Cd), 46.4 (C8), 48.5 (C4), 52.8, 53.7, and
54.2 (C2, C9, Ce), 67.8 (C1).
1,3-Dibromo-5-ethyl-7-hexyladamantane
The reaction was performed following general procedure C,
starting from 1-ethyl-3-hexyladamantane (17.9 g, 72.0 mmol)
to yield 1,3-dibromo-5-ethyl-7-hexyladamantane as pale yellow
oil (13.0 g, 32.0 mmol, 44%) after purification with column
chromatography (silica gel, hexane). Ethyl and hexyl groups:
C(b)H2C(a)H3, C(c)H2C(d)H2C(e)H2C(f)H2C(g)H2C(h)H3.
1H NMR (300 MHz, CDCl3): d 0.83–0.93 (m, 6H, C(a)H3,
C(h)H3), 1.24–1.29 (m, 14H, C(6)H2, C(b)H2, C(c)H2¸C(d)H2,
C(e)H2, C(f)H2¸C(g)H2), 1.94–2.06 (m, 8H, C(4)H2, C(8)H2,
C(9)H2, C(10)H2), 2.75 (s, 2H, C(2)H2). 13C NMR (75 MHz,
CDCl3): d 7.3 (Ca), 14.3 (Ch), 22.7, 22.8, 30.0, and 31.9 (Cd,
Ce, Cf, Cg), 34.8 (Cb), 41.5 and 41.6 (C5, C7), 42.7 (Cc), 43.7
(C6), 51.3 and 51.7 (C4, C8, C9, C10), 58.3 (C2), 62.7 (C1,
C3). IR (neat, cm21): 2926, 2853, 1457, 1332, 1313, 1156,
959, 882, 844, 749, 714.
General Procedure C: Dibromination of
1-Alkyladamantanes with Br2/AlBr3
1,3-Dibromo-5-hexyladamantane
The reaction was performed according to our previous
report.10c A mixture of 1-hexyladamantane (16.8 g, 76.2
mmol) and bromine (30 mL) was stirred at room tempera-
ture for 24 h to prepare 1-bromo-3-hexyladamantane. Alumi-
num foil (80 mg, 2.97 mmol) was reacted with bromine (10
mL) in another flask, and it was added dropwise to the bro-
mine solution of 1-bromo-3-hexyladamantane at 0 ꢀC. The
reaction mixture was stirred at 0 ꢀC for 3 h and was care-
1,3-Dibromo-5-butyl-7-hexyladamantane
The reaction was performed following general procedure C,
starting from 1-butyl-3-hexyladamantane (4.58 g, 16.6
mmol) to yield 1,3-dibromo-5-butyl-7-hexyladamantane as
pale yellow oil (4.41 g, 10.2 mmol, 61%) after purification
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fully poured into aqueous NaHSO3 solution at 0 C to quench
excess amount of bromine. The aqueous layer was extracted
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 4111–4124