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S.V. Mulpuri et al. / Polymer 52 (2011) 4377e4386
2.3.6. 2,3-bis-Benzyloxymethyl-norbornene (2a)
d
¼ 173.6, 137.9, 61.1, 47.4, 45.5, 42.5, 42.3, 37.0, 31.7, 28.7. MALDI-
At
0
ꢀC, 2,3-bis(hydroxymethyl)-5-norbornene (5.87 g,
TOF MS: m/z calcd for C33H46O4, 506.3; found, 529.0 [M þ Na]þ.
0.038 mol) was dissolved in DMF under Ar. NaH (2.27 g, 0.095 mol)
was added slowly to the solution with gentle stirring. After 1 h,
benzyl bromide (11.3 g, 0.095 mol) was added and the solution
temperature was increased slowly to room temperature. After
24 h, the reaction was quenched by gradual addition of cold water.
The solution was diluted with excess amount of ethyl acetate. The
organic layer was washed with water, dried with MgSO4, filtered,
and concentrated in a rotary evaporator. The crude product was
further purified in a silica gel column chromatography using ethyl
acetate/hexane (1:1, v/v). Yield: 9.26 g (71%). 1H NMR (CDCl3):
2.3.11. cis-Norbornene-exo-2,3-dicarboxylic acid
dinorbornanemethyl ester (1f)
The same procedure described above was employed to the
mixture of 1 (3.00 g, 18.3 mmol), p-TsOH (0.17 g, 0.91 mmol), nor-
bornane-2-methanol (5.45 g, 38.4 mmol), and toluene (100 mL).
The crude product was further purified in a silica gel column
chromatography using ethyl acetate/hexane (1:4, v/v) to give
a yellowish white solid product. Yield: 4.52 g (62.1%); mp: 75e77 ꢀC
1H NMR (CDCl3):
2.60 (s, 2H), 2.19e2.21(m, 6H), 1.47e1.54 (m, 12H), 1.31e1.08 (m,
4H), 0.64e0.66 (d, 2H). 13C NMR (CDCl3):
d
¼ 6.20 (s, 2H), 3.82e4.02 (m, 4H), 3.07 (s, 2H),
d
¼ 7.41 (m, 10H), 6.23 (s, 2H), 4.55 (s, 4H), 3.69e3.76 (m, 2H),
3.42e4.46 (t, 2H), 2.99 (s, 2H), 1.93 (s, 2H), 1.55 (d, 1H),
1.30e1.37(d, 1H).
d
¼ 173.6, 138.0, 66.7, 47.4,
45.8, 39.8, 38.7, 38.4, 36.7, 33.8, 29.9, 29.7, 22.7. MALDI-TOF MS: m/z
calcd for C25H34O4, 398.2; found, 421.0 [M þ Na]þ.
2.3.7. Toluene-4-sulfonic acid 3-phenylpropyl ester
To a solution of 3-phenyl-1-propanol (5.00 g, 0.037 mmol) and
p-TsCl (8.39 g, 0.044 mmol) in dichloromethane (50 mL), TEA (1.2
equiv., 4.4 mL) was added. The mixture was stirred for 5 h at room
temperature and the reaction was monitored by thin layer chro-
matography (TLC). Upon completion, the mixture was filtered
through a filter paper and the filtrate was concentrated in a rotary
evaporator. The crude product was further purified in a silica gel
column chromatography using ethyl acetate/hexane (1:10, v/v).
2.3.12. cis-Norbornene-exo-2,3-dicarboxylic acid
dinorbornaneethyl ester (1g)
The same procedure described above was employed to the
mixture of 1 (3.00 g, 18.3 mmol), p-TsOH (0.17 g, 0.91 mmol), nor-
bornane-2-ethanol (5.37 g, 38.4 mmol), and toluene (100 mL). The
crude product was further purified in a silica gel column chroma-
tography using ethyl acetate/hexane (1:2, v/v) to give an oily
product. Yield: 5.24 g (67.2%). 1H NMR (CDCl3):
d
¼ 6.17 (s, 2H),
3.93e4.03 (m, 4H), 3.0 (s, 2H), 2.5 (s, 2H), 2.16 (s, 2H), 2.13 (d, 1H),
1.92 (s, 2H), 1.06e1.58 (m, 27H). 13C NMR (CDCl3):
Yield: 9.8 g (91.8%). 1H NMR (CDCl3):
6.62e6.71 (m, 3H), 6.50e6.53 (d, 2H), 3.46e3.50 (t, 2H), 2.07e2.12
(t, 2H), 1.90 (s, 3H), 1.36e1.45 (m, 2H). 13C NMR (CDCl3):
d
¼ 7.25 (s, 2H), 6.77 (d, 2H),
d
¼ 174.0, 138.4,
d
¼ 145.2,
64.1, 47.8, 46.1, 41.6, 41.5, 39.1, 38.5, 37.0, 36.0, 35.8, 30.5, 29.2.
MALDI-TOF MS: m/z calcd for C27H38O4, 426.3; found, 449.0
[M þ Na]þ.
140.81, 133.5, 130.3, 128.9, 128.3, 126.5, 70.0, 31.8, 30.8, 22.0.
2.3.8. 2,3-bis-Phenyl-propoxymethyl-norbornene (2b)
The same procedure described above was employed to the
mixture of 2,3-bis(hydroxymethyl)-5-norbornene (1.31 g,
8.49 mmol), toluene-4-sulfonic acid 3-phenyl-propyl ester (6.1 g,
0.021 mol), NaH (0.84 g, 0.021 mol) and DMF (100 mL). The crude
product was further purified in a silica gel column chromatography
using ethyl acetate/hexane (1:4, v/v) to give an oily product. Yield:
2.3.13. Norbornane-2-ethanol
2-norbornane acetic acid (12 g, 77.8 mmol) was dissolved in
anhydrous THF (120 mL) and treated dropwise with LiAlH4 (diluted
in THF) at 0 ꢀC. The reaction was stirred for three days, and then
quenched by a dropwise addition of water (50 mL). The reaction
mixture was diluted with diethyl ether (250 mL) and washed with
water (3 ꢁ 150 mL). The combined organic extracts were dried over
MgSO4, filtered, and concentrated in a rotary evaporator to yield an
oily product. The product was passed through a pad of silica gel to
yield norbornane-2-ethanol as a colorless oil (10 g, 91%). 1H NMR
2.7 g (81.3%). 1H NMR (CDCl3):
d
¼ 7.33e7.40 (m, 10H), 6.21 (s, 2H),
3.59 (m, 2H), 3.43(m, 4H), 3.35 (m, 2H), 2.82 (s, 2H), 2.73 (m, 4H),
1.96 (m, 4H), 1.84 (s, 2H), 1.61(d, 1H), 1.34 (d, 1H). 13C NMR (CDCl3):
d
¼ 141.9, 137.4, 128.5, 128.4, 125.8, 72.2, 70.2, 44.9, 40.6, 32.5, 31.4.
(CDCl3):
d
¼ 3.55e3.60 (t, 2H), 2.15 (s, 1H), 1.91 (s, 1H),1.24e1.46 (m,
2.3.9. cis-Norbornene-exo-2,3-dicarboxylic acid
diadamantylmethyl ester (1d)
8H), 1.02e1.10 (t, 4H). 13C NMR (CDCl3):
d
¼ 61.3, 41.1, 39.9, 38.4,
38.1, 36.5, 35.3, 30.0, 28.8.
The same procedure described above was employed to the
mixture of 1 (1.90 g, 11.6 mmol), p-TsOH (0.09 g, 0.57 mmol), ada-
mantane-2-methanol (4.04 g, 24.3 mmol), and toluene (80 mL). The
crude product was further purified in a silica gel column chroma-
tography using ethyl acetate/hexane (1:4, v/v) to give a white solid
product. Yield: 3.26 g (60%). mp: 154e156 ꢀC 1H NMR (CDCl3):
2.3.14. 6-Phenyl-1-hexene
1-bromo-3-phenylpropane (126 g, 0.63 mol) solution in 250 mL
diethyl ether was added dropwise to a magnesium (19 g, 0.78 mol)
and iodine activation solution in 250 mL diethyl ether. The solution
was stirred for 1 h at room temperature under nitrogen. After
dropwise addition of allyl bromide (106 g, 0.88 mol) in diethyl
ether, the solution was heated to reflux for 2.5 h. The reaction was
quenched with 200 g of ice water. The organic layer was washed
with water, dried with sodium sulfate, filtered, and concentrated in
a rotary evaporator. The crude product was purified with vacuum
distillation. Yield: 96.1 g (95%); bp: 64 ꢀC, 0.9 mbar. 1H NMR
d
¼ 6.24 (s, 2H), 3.70 (d, 2H), 3.53 (d, 2H), 3.11(s, 2H), 2.66 (s, 2H),
2.15 (d, 1H), 1.99 (d, 1H), 1.76e1.25 (m, 30H). 13C NMR (CDCl3):
d
¼ 173.1, 137.4, 74.0, 46.9, 45.3, 45.0, 38.8, 36.5, 32.5, 27.6. MALDI-
TOF MS: m/z calcd for C31H42O4, 478.3; found, 501.0 [M þ Na]þ.
2.3.10. cis-Norbornene-exo-2,3-dicarboxylic acid diadamantylethyl
ester (1e)
(CDCl3):
d
¼ 7.02e7.27 (m, 5H), 5.64e5.79 (m, 1H), 4.82e4.96 (m,
The same procedure described above was employed to the
mixture of 1 (2.00 g, 12.2 mmol), p-TsOH (0.09 g, 0.60 mmol),
adamantane-2-ethanol (4.61 g, 25.6 mmol), and toluene (80 mL).
The crude product was further purified in a silica gel column
chromatography using ethyl acetate/hexane (1:4, v/v) to give
a white solid product. Yield: 3.91 g (63.3%). mp: 70e74 ꢀC 1H NMR
2H), 2.52 (t, 2H), 1.94e2.06 (m, 2H), 1.55 (qui, 2H), 1.35 (t, 2H). 13C
NMR (CDCl3):
30.9, 28.5.
d
¼ 142.6, 138.8, 128.4, 128.2, 125.6, 114.4, 35.8, 33.6,
2.3.15. 2-(4-Phenylbutyl)-5-norbornene (3a)
A 150 mL stainless steel autoclave vessel was charged with
dicyclopentadiene (46.6 g, 0.35 mol) and 6-phenyl-1-hexene (113 g,
0.71 mol) under argon atmosphere. The reaction mixture was
(CDCl3):
d
¼ 6.15 (s, 2H), 3.99e4.17 (m, 4H), 3.06 (s, 2H), 2.56 (s, 2H),
2.11e2.13 (d, 1H), 1.93 (s, 5H), 1.24e1.71 (m, 30H). 13C NMR (CDCl3):