1
10
S. Pu et al. / Journal of Molecular Structure 919 (2009) 100–111
the reaction mixture, and kept stirring for 2 h at ꢀ78 °C under
nitrogen atmosphere. Then the reaction mixture was extracted
with diethyl ether and evaporated in vacuum. The residue was
1H NMR (CDCl
0.94–0.97 (m, 2H, –CH
J = 7.5 Hz, –CH ), 2.00–2.08 (m, 1H, –CH
–CH ), 2.42–2.48 (m, 1H, –CH ), 2.64–2.70 (m, 1H, –CH
2
3
, 400 MHz, TMS): d 0.65 (t, 3H, J = 6.7 Hz, –CH
), 1.24–1.26 (m, 2H, –CH ), 1.07 (t, 3H,
), 2.27–2.32 (m, 1H,
), 3.97–
3
),
2
2
3
2
purified by column chromatography on silica gel to give 5.16 g of
2
2
1
7
c in 54.7%. H NMR (CDCl
3
, 400 MHz, TMS): d 1.37 (t, 3H,
4.04 (m, 4H, dioxolane-H), 5.96 (s, 1H, dioxolane-H), 7.04 (s, 1H,
J = 7.5 Hz, –CH
3
), 2.82–2.88 (m, 2H, –CH ), 7.36–7.41 (m, 2H, phe-
2
thienyl-H), 7.32–7.35 (m, 2H, phenyl-H), 7.60 (d, 1H, J = 7.8 Hz,
1
3
nyl-H), 7.48 (d, 1H, J = 7.6 Hz, phenyl-H), 7.82 (d, 1H, J = 7.6 Hz,
phenyl-H), 7.75 (d, 1H, J = 7.7 Hz, phenyl-H). C NMR (CDCl
3
,
phenyl-H).
100 MHz, TMS): d 13.56, 15.34, 21.97, 22.75, 33.47, 38.59, 65.14,
6
5.20, 99.86, 118.84, 122.20, 122.36, 122.43, 122.63, 124.43,
ꢀ1
4.1.1.4. 1-(2-Ethyl-3-benzothienyl)-2-{2-methyl-5-[2-(1,3-dioxolane)]-3-
124.85, 125.88, 136.93, 138.21, 141.12, 150.03. IR (KBr, m, cm ):
thienyl}perfluorocyclopentene 1a. To a stirred THF solution (30 mL) con-
taining 4-bromo-2-methyl-5-(1,3-dioxolane)thiophene (4c) [35]
731, 758, 783, 953, 989, 1031, 1072, 1116, 1140, 1188, 1251,
1274, 1343, 1384, 1460, 1558, 1630, 2957. Calcd for C26
(%): Calcd C, 57.13; H, 4.43. Found: C, 57.31; H, 4.14.
24 6 2 2
H F O S
(2.04 g, 8.20 mmol) was slowly added 3.31 mL n-BuLi (1.6 M) at
ꢀ
78 °C under nitrogen atmosphere. After 40 min, 10 mL THF solution
containing compound 7c 2.79 g (8.20 mol) was added slowly to the
reaction mixture, and kept stirring for 2 h at ꢀ78 °C under nitrogen
atmosphere. Then the reaction mixture was extracted with diethyl
ether and evaporated in vacuum. The residue was purified by column
chromatography on silica gel to give 1.65 g of 1a in 40.1%. 1H NMR
4.1.1.8. 1-(2-Ethyl-3-benzothienyl)-2-{2-n-amyl-5-[2-(1,3-dioxolane)]-3-
thienyl}perfluorocyclopentene (5a). Compound 5a were prepared by a
1
method similar to that used for 1a (44.31% yield). H NMR (CDCl
3
,
400 MHz, TMS): d 0.74 (t, 3H, J = 7.1 Hz, -CH
-CH ), 1.07 (t, 3H, J = 7.5 Hz, –CH ), 1.26–1.27 (m, 2H, –CH
2.05 (m, 1H, –CH ), 2.24–2.28 (m, 1H, –CH ), 2.43–2.45 (m, 1H, –CH
2.65–2.67 (m, 1H, –CH ), 3.96–4.05 (m, 4H, dioxolane-H), 5.96 (s, 1H,
3
), 0.98–1.01 (m, 4H,
), 2.03–
),
2
3
2
(
CDCl
J = 7.5 Hz, –CH
.97–4.04 (m, 4H, dioxolane-H), 5.96 (s, 1H, dioxolane-H), 7.03 (s,
3
, 400 MHz, TMS): d 0.7 (t, 3H, J = 7.5 Hz, –CH
3
), 1.09 (t, 3H,
2
2
2
3
), 2.47–2.53 (m, 1H, –CH ), 2.68–2.73 (m, 1H, –CH
2
2
),
2
3
dioxolane-H), 7.03 (s, 1H, thienyl-H), 7.33–7.38 (m, 2H, phenyl-H),
1
H, thienyl-H), 7.26–7.35 (m, 2H, phenyl-H), 7.55 (d, 1H, J = 7.7 Hz,
7.60 (d, 1H, J = 7.1 Hz, phenyl-H), 7.75 (d, 1H, J = 7.8 Hz, phenyl-H).
C NMR (CDCl , 100 MHz, TMS): d 13.70, 15.33, 22.19, 22.73, 29.23,
3
13
13
phenyl-H), 7.75 (d, 1H, J = 7.6 Hz, phenyl-H).
C NMR (CDCl
3
,
1
1
1
1
1
00 MHz, TMS): d 14.37, 14.88, 22.30, 64.57, 64.65, 99.21, 118.39,
21.68, 121.80, 123.15, 123.93, 124.37, 125.78, 137.66, 139.04,
30.96, 31.04, 65.15, 65.21, 99.87, 118.85, 122.21, 122.40, 122.47,
122.62, 124.42, 124.83, 125.86, 138.22, 138.31, 139.66, 150.10,
ꢀ1
ꢀ1
42.87, 149.61. IR (KBr,
006, 1023, 1078, 1123, 1156, 1174, 1196, 1269, 1334, 1367, 1436,
459, 1564, 1634, 2977. Anal. Calcd for C23 (%): Calcd C,
4.76; H, 3.60. Found: C, 55.08; H, 3.37.
m, cm ): 731, 760, 779, 850, 898, 947, 979,
150.22. IR (KBr,
m
, cm ): 731, 754, 942, 970, 989, 1018, 1073, 1100,
1141, 1190, 1275, 1343, 1435, 1458, 1640, 3930, 2954. Calcd for
C H F O S (%): Calcd C, 57.85; H, 4.67. Found: C, 58.01; H, 4.48.
27 26 6 2 2
H
18
F
6
O
2
S
2
5
4
.1.1.9. 1-(2-Ethyl-3-benzothienyl)-2-{2-n-hexyl-5-[2-(1,3-dioxolane)]-3-
4
3
.1.1.5. 1-(2-Ethyl-3-benzothienyl)-2-{2-ethyl-5-[2-(1,3-dioxolane)]-
thienyl}perfluorocyclopentene (6a). Compound 6a were prepared by a
-thienyl}perfluorocyclopentene (2a). Compound 2a were prepared
1
method similar to that used for 1a (42.10% yield). H NMR (CDCl
00 MHz, TMS): d 0.81 (t, 3H, J = 7.5 Hz, –CH ), 0.93–0.98 (m, 4H,
CH ), 1.08 (t, 3H, J = 7.6 Hz, –CH ), 1.12–1.16 (m, 2H, –CH ), 1.24–
.26 (m, 2H, –CH ), 2.00–2.03 (m, 1H, –CH ), 2.24–2.30 (m, 1H, –
CH ), 2.41–2.47 (m, 1H, –CH ), 2.63–2.69 (m, 1H, –CH ), 3.96–4.05
m, 4H, dioxolane-H), 5.96 (s, 1H, dioxolane-H), 7.05 (s, 1H, thienyl-
H), 7.33–7.39 (m, 2H, phenyl-H), 7.60 (d, 1H, J = 7.8 Hz, phenyl-H),
3
,
1
by a method similar to that used for 1a (43.50% yield). H NMR
4
–
1
3
(
CDCl
3
, 400 MHz, TMS): d 0.72 (t, 3H, J = 7.5 Hz, –CH
H, J = 7.5 Hz, –CH ), 2.18–2.23 (m, 1H, –CH ), 2.36–2.41 (m, 1H,
CH ), 2.46–2.50 (m, 1H, –CH ), 2.66–2.70 (m, 1H, –CH ), 3.97–
.04 (m, 4H, dioxolane-H), 5.96 (s, 1H, dioxolane-H), 7.03 (s, 1H,
3
), 1.10 (t,
2
3
2
3
–
4
3
2
2
2
2
2
2
2
2
2
(
thienyl-H), 7.26–7.35 (m, 2H, phenyl-H), 7.56 (d, 1H, J = 7.9 Hz,
phenyl-H), 7.75 (d, 1H, J = 7.7 Hz, phenyl-H). 13C NMR (CDCl
3
,
13
7
1
1
.75 (d, 1H, J = 7.8 Hz, phenyl-H). C NMR (CDCl
2.92, 14.33, 21.38, 21.76, 27.55, 28.28, 30.33, 64.16, 64.23, 98.90,
17.89, 121.21, 121.41, 121.48, 121.66, 123.45, 123.72, 123.85,
3
, 100 MHz, TMS): d
1
1
1
9
2
3
00 MHz, TMS):
d 15.35, 15.43, 22.64, 22.82, 65.16, 65.23,
15.90, 118.80, 122.21, 122.45, 124.44, 124.88, 125.99, 137.30,
ꢀ
1
38.29, 139.69, 150.18, 151.26. IR (KBr,
m
, cm ): 733, 762, 932,
ꢀ1
1
7
1
24.87, 137.24, 137.34, 138.70, 149.10, 149.23. IR (
54, 984, 1021, 1076, 1140, 1193, 1274, 1344, 1384, 1459, 1565,
678, 2929, 3065. Calcd for C28 (%): Calcd C, 58.52; H, 4.91.
m, cm ): 730,
91, 1082, 1138, 1190, 1271, 1340, 1433, 1458, 1560, 1633,
893, 2978. Anal. Calcd for C24
.89. Found: C, 55.74; H, 3.67.
20 6 2 2
H F O S (%): Calcd C, 55.59; H,
28 6 2 2
H F O S
Found: C, 58.76; H, 4.73.
4
.1.1.6. 1-(2-Ethyl-3-benzothienyl)-2-{2-n-propyl-5-[2-(1,3-dioxolane)]-3-
thienyl}perfluorocyclopentene (3a). Compound 3a were prepared by a
method similar to that used for 1a (44.20% yield). 1H NMR (CDCl
00 MHz, TMS): d 0.51 (t, 3H, J = 7.3 Hz, –CH ), 1.08 (t, 3H, J = 7.4 Hz,
CH ), 1.26–1.34 (m, 2H, –CH ), 2.00–2.06 (m, 1H, –CH ), 2.20–2.26
m, 1H, -CH ), 2.45–2.49 (m, 1H, –CH ), 2.65–2.70 (m, 1H, –CH ),
.96–4.03 (m, 4H, dioxolane-H), 5.96 (s, 1H, dioxolane-H), 7.03 (s, 1H,
thienyl-H), 7.32–7.37 (m, 2H, phenyl-H), 7.59 (d, 1H, J = 7.9 Hz, phe-
nyl-H), 7.74 (d, 1H, J = 7.8 Hz, phenyl-H). 13C NMR (CDCl
, 100 MHz,
TMS): d 13.20, 15.36, 22.75, 24.49, 31.17, 65.14, 65.20, 99.85, 118.82,
22.21, 122.37, 122.44, 122.68, 124.43, 124.84, 125.93, 138.22, 138.23,
4.2. Crystallography
3
,
4
–
(
3
3
Crystal data of diarylethenes were collected by a Bruker SMART
APEX2 CCD area-detector equipped with graphite monochroma-
3
2
2
tized Mo K
coefficients,
a
radiation at room temperature. The linear absorption
, of diarylethenes 2a–6a for Mo K radiation 2.97,
2
2
2
l
a
ꢀ
1
2.88, 2.75, 2.69 and 2.57 cm . Direct phase determination yielded
the positions of all non-hydrogen atoms. All non-hydrogen atoms
were subjected to anisotropic refinement. All hydrogen atoms
were generated geometrically with CAH bond distances of 0.93–
0.97 Å according to criteria described in the SHELXTL manual. They
were included in the refinement with Uiso(H) = 1.2Ueq(C) or
1.5Ueq(methyl C). Further details on the crystal structure investi-
gation have been deposited to The Cambridge Crystallographic
Data Centre as supplementary publication number CCDC 661183
for 2a, 661185 for 3a, 661186 for 4a, 661184 for 5a and 661187
3
1
ꢀ1
1
1
1
39.68, 149.75, 150.19. IR (KBr,
016, 1073, 1099, 1120, 1137, 1191, 1271, 1338, 1384, 1438, 1571,
677, 2889, 2972. Calcd for C25 (%): Calcd C, 56.38; H, 4.16.
Found: C, 56.47; H, 4.02.
m, cm ): 729, 753, 768, 935, 986,
22 6 2 2
H F O S
4.1.1.7. 1-(2-Ethyl-3-benzothienyl)-2-{2-n-butyl-5-[2-(1,3-dioxo-
lane)]-3-thienyl}perfluorocyclopentene (4a). Compound 4a were
prepared by a method similar to that used for 1a (41.62% yield).