ACCEPTED MANUSCRIPT
silica gel column chromatography with 75:25 hex-
anes/ethyl acetate as eluent to give the title compound as
a pale yellow oil (0.5515 g, 48.97% yield).
4.746 mmol), anhydrous silica gel (20.13 g), and iso-
prene (5.8 mL, 58 mmol) was stirred at room tempera-
ture for 18 h. The reaction flask was equipped with a
Findenser™ to minimize evaporation of isoprene. Di-
chloromethane (200 mL) was added to the reaction mix-
ture, and then filtered. The filtrate was concentrated in
vacuo and bubbled with air for 3 d to give the title com-
pound as a yellow oil (2.011, 96.14% yield).
TLC: 75:25 hexanes/ethyl acetate, p-anisaldehyde stain,
R : 0.33.
f
1
H NMR (500 MHz, CDCl ): δ 7.74 (d, J = 7.9 Hz, 1H),
3
7
4
.70 (d, J = 1.5 Hz, 1H), 7.53 (dd, J = 7.9, 1.5 Hz, 1H),
.67 (s, 2H), 4.21 (d, J = 2.5 Hz, 2H), 3.41 (s, 3H), 3.40
(
s, 3H), 2.76 (t, J = 2.5 Hz, 1H).
TLC: 90:10 hexanes/ethyl acetate, p-anisaldehyde stain,
13
C NMR (125 MHz, CDCl , DEPT): δ 168.2 (C=O),
f
R : 0.66.
3
1
1
(
7
67.8 (C=O), 141.1 (4°), 132.5 (4°), 131.1 (4°), 130.0
CH), 129.3 (CH), 127.9 (CH), 79.2 (CH), 75.3 (4°),
0.4 (CH ), 57.7 (CH ), 52.8 (CH ), 52.7 (CH ).
H NMR (500 MHz, CDCl , two diastereomers): δ 7.65
3
(d, J = 8.0 Hz, 1H), 7.44 (d, J = 1.7 Hz, 1H), 7.31 (dd, J
= 8.0, 1.7 Hz, 1H), 4.25 – 4.11 (m, 4H), 2.42 (s, 3H),
1.75 – 1.49 (m, 2H), 1.51 – 1.18 (m, 16H), 1.02 – 0.77
2
2
3
3
FTIR: 2931 (aliphatic C-H stretch), 2120 (alkyne C-C
stretch), 1727 (C=O stretch), 1462 (aromatic C=C
stretch), 1287 (C-O stretch) cm
(m, 12H).
-1
13
3
C NMR (125 MHz, CDCl , DEPT, two diastereomers):
Preparation of bis(2-ethylhexyl) 4-((prop-2-yn-1-
yloxy)methyl)phthalate (14). To a stirred solution of 2-
ethylhexanol (0.4398 g, 3.377 mmol) in 5 mL of anhy-
drous tetrahydrofuran was added sodium hydride
δ 168.5 (C=O), 167.5 (C=O), 141.9 (4°), 133.3 (4°),
131.3 (CH), 129.9 (CH), 129.3 (4°), 67.9 (CH ), 67.6
2
(CH ) 38.8 (CH), 38.7 (CH), 30.4 (CH ), 30.2 (CH ),
2
,
2
2
28.8 (CH
2
), 28.7 (CH
2
), 23.7 (CH
2
), 23.5 (CH
2
), 21.3
(
0.3402 g, 7.091 mmol, 60% suspension in mineral oil)
(CH ), 14.1 (CH ), 11.0 (CH ).
3
3
3
at room temperature and stirred for 5 minutes. A solu-
tion of dimethyl 4-((prop-2-yn-1-yloxy)methyl)
phthalate 13 (0.4428 g, 1.688 mmol) in 5 mL of anhy-
drous tetrahydrofuran was added at room temperature,
and stirred for 1 h. The reaction mixture was cooled to 0
FTIR: 2953 (C-H stretch), 1728 (C=O stretch), 1435 (C-
H scissoring), 1294 (C-O stretch) cm .
-1
Preparation of bis(2-ethylhexyl) 4-(bromomethyl)-
phthalate (16). To a stirred solution of bis(2-ethylhexyl)
4-methylphthalate 15 (0.3681 g, 0.9098 mmol) and N-
bromosucinimide (0.1943 g, 0.0273 mmol) in 10 mL of
benzene was added benzoyl peroxide (0.0039 g, 1.991
mmol) at room temperature. The reaction mixture was
refluxed for 3 d using a Dean-Stark apparatus. The reac-
tion mixture was concentrated in vacuo to evaporate
benzene. The resulting yellow oil (0.2221 g) was puri
fied by Biotage gradient chromatography using hex-
anes/ethyl acetate as eluent, to give the title compound
as a pale yellow oil (0.1511 g, 32.29% yield).
°C, and then quenched with 3 mL of saturated ammoni-
um chloride solution. The organic layer was separated
and the aqueous layer was extracted three times with 10
mL of chloroform. The combined organic layer was
washed two times with 10 mL of brine, dried over
MgSO and concentrated in vacuo. The resulting red oil
4
(
0.8178 g) was purified by silica gel column chromatog-
raphy with 75:25 hexanes/ethyl acetate as eluent, to give
the title compound as a pale yellow oil (0.2414 g,
3
1.18% yield).
TLC: 75:25 hexanes/ethyl acetate, p-anisaldehyde, Rf:
.77.
TLC: 90:10 hexanes/ethyl acetate, p-anisaldehyde stain,
R : 0.40.
f
1
0
H NMR (500 MHz, CDCl two diastereomers): δ 7.69
3
,
1
H NMR (500 MHz, CDCl two diastereomers): δ 7.72
(d, J = 1.8 Hz, 1H), 7.58 (d, J = 7.5 Hz, 1H), 7.55 (dd,
J= 7.5, 1.8 Hz, 1H), 4.49 (s, 2H), 4.29 - 4.12 (m, 4H),
1.68 (m, 2H), 1.48 - 1.18 (m, 16H), 0.81 - 0.91 (m,
12H).
3,
(
=
d, J = 7.9 Hz, 1H), 7.66 (d, J = 1.7 Hz, 1H), 7.52 (dd, J
7.9, 1.7 Hz, 1H), 4.67 (s, 2H), 4.31 - 4.11 (m, 6H),
2
1
.49 (t, J = 2.5 Hz, 1H), 1.68 (m, 2H), 1.47 - 1.20 (m,
6H), 0.99 - 0.81 (m, 12H).
1
3
3
C NMR (125 MHz, CDCl , DEPT, two diastere-
13
C NMR (125 MHz, CDCl , DEPT, two diastere-
omers): δ (167.8 (C=O), 167.7 (C=O), 141.4 (4°), 133.7
3
omers): δ 167.9 (C=O), 167.5 (C=O), 141.1 (4°), 133.1
4°), 131.6 (4°), 129.9 (CH), 129.3 (CH), 127.9 (CH),
9.2 (CH), 75.2 (4°), 70.4 (CH ), 68.3 (CH ), 68.2
CH ), 57.6 (CH ), 38.8 (CH), 31.9 (CH ), 30.4 (CH ),
(4°), 132.6 (4°), 131.9 (CH), 129.9 (CH), 129.8 (CH),
(
7
(
68.9 (CH
(CH ), 29.3 (CH
11.4 (CH3).
FTIR: 2930 (C-H stretch), 1728 (C=O stretch), 1463 (C-
2
), 68.7 (CH
2
), 39.12 (CH), 31.9 (CH
2
), 30.8
2
2
2
2
), 24.2 (CH
2
), 23.4 (CH ), 14.5 (CH
2
3
),
2
2
2
2
2
8.9 (CH ), 23.7 (CH ), 23.0 (CH ), 14.1 (CH ), 11.0
2 2 2 3
-1
(
CH
3
).
H scissoring), 1288 (C-O stretch) cm .
FTIR: 2931 (aliphatic C-H stretch), 2120 (alkyne C-C
stretch), 1727 (C=O stretch), 1462 (aromatic C=C
HRMS: calcd. for C H BrO [M-H]: 481.1958: found
481.1955.
29
35
4
-1
stretch), 1287 (C-O stretch) cm .
HRMS: calcd. for C H O [M+H] : 459.3105: found
Preparation of 4-bromomethylphthalic anhydride
(17). To a stirred solution of 4-methylphthalic anhydride
and N-bromosuccinimide (5.601 g, 31.47 mmol) in
100 mL of acetonitrile was added dibenzoyl peroxide
(0.1345 g, 0.9441 mmol) at room temperature. The reac-
tion mixture was refluxed for 24 h. The reaction mixture
+
28
42
5
4
59.3075.
Preparation of bis(2-ethylhexyl) 4-methylphthalate
15). Following the procedure of Smit et al. [30] a mix-
ture of 2-ethylhexylacetylene dicarboxylate (1.739 g,
(
1
1