Conjugated Helical Acetylene-Bridged Polymers and Cyclophanes
J . Org. Chem., Vol. 63, No. 6, 1998 2037
(m, 2H), 1.8-1.2 (m, 24H), 0.86 (m, 6H) ppm; 13C NMR (CDCl
,
3
2
H, J ) 8.1 Hz), 7.90 (d, 2H, J ) 8.5 Hz), 7.86 (d, 2H, J ) 8.5
Hz), 7.79 (d, 2H, J ) 8.0 Hz), 7.42 (s, 2H), 7.18 (d, 2H, J ) 8.0
75 MHz): δ 170.27, 142.92, 139.06, 129.75, 128.04, 127.21,
92.82, 48.50, 44.64, 31.80, 31.65, 29.37, 29.28, 28.94 (2 peaks),
28.31, 27.26, 27.10, 26.54, 22.62, 22.55, 14.09 ppm; HRMS
calcd for C23H38INO (M + 1) 472.2076, found 472.2072.
1,2-Bis(N,N-d ioctylca r ba m oyl)-4,5-d iiod oben zen e (3).
Hz), 4.04 (d, 2H, J ) 12.4 Hz), 3.88 (d, 2H, J ) 12.4 Hz), 0.53
1
3
(s, 2H) ppm; C NMR (CDCl3, 75 MHz): δ 137.35, 133.15,
1
1
3
31.67, 131.10, 129.53, 127.58, 127.4-127.2 (m), 126.95,
26.88, 124.84, 123.93, 65.23 ppm; HRMS calcd for C28
88.1463, found 388.1472.
H
20
O
2
CH Cl2 (10 mL) and dioctylamine (0.419 g, 0.525 mL, 1.74
2
(
+)-[6]Helicen e-2,15-d ica r boxa ld eh yd e (11). The Dess-
mmol) were sequentially added to a flask containing DCC
(0.239 g, 1.16 mmol), DMAP (0.212 g, 1.74 mmol), DMAP‚-
HCl36 (0.239 g, 1.51 mmol), and 4,5-diiodophthalic anhydride
(0.232 g, 0.58 mmol). The mixture was refluxed for 3 h and
then cooled to room temperature. Additional CH Cl was
2
1b
Martin periodinane
solution of (+)-10a (0.112 g, 0.289 mmol) in CH
After stirring for 45 min, CH Cl was added, followed by four
washes with 10% Na , four with saturated sodium bicar-
bonate, and one with water, each time back extracting with a
small amount of CH Cl . Drying (Na SO ), solvent removal,
and drying in vacuo gave 0.109 g (98%) of (+)-11, a yellow solid,
mp > 220 °C. [R] +6060 (c 0.005, CH Cl ); IR(KBr): 3046,
815, 2710, 1687, 1601 cm- ; H NMR (CDCl
, 400 MHz): δ
(0.367 g, 0.866 mmol) was added to a
24
2
2
Cl (4 mL).
2
2
2
2 3
S O
2
2
added, followed by washes with HCl (1 M) and sat. NaHCO3,
drying (Na SO ), solvent removal and chromatography (12 in.
2
2
2
4
2
4
× 1 in., eluting first with 3:1 CH Cl /hexane, and then CH -
2
2
2
D
2
2
2 2 2
Cl , and finally with 3:1 CH Cl /acetone). Fractions containing
1
1
2
9
8
7
3
2 2
compound 3 were pale yellow and eluted with CH Cl /acetone.
Adding hexane to the residue and filtering through Celite
removed an impurity and gave 0.420 g (84%) of 3, a waxy
semisolid. IR(neat): 2926, 2855, 1642, 1466, 1426 cm ; H
.14 (s, 2H), 8.14 (d, 2H, J ) 8.7 Hz), 8.12 (d, 2H, J ) 8.1 Hz),
.08 (d, 2H, J ) 8.1 Hz), 7.99 (d, 2H, J ) 8.5 Hz), 7.94 (s, 2H),
.90 (d, 2H, J ) 8.1 Hz), 7.65 (d, 2H, J ) 8.1 Hz) ppm; 13
C
-1
1
NMR (CDCl3, 75 MHz): δ 191.45, 135.35, 134.01, 133.75,
32.65, 131.89, 129.89, 128.86, 128.70, 127.94, 127.79 (2
peaks), 127.57, 123.53, 122.92 ppm; HRMS calcd for C28
84.1151, found 384.1150.
+)-2,15-Bis(2-ch lor oeth en yl)[6]h elicen e (11a ). Lithium
NMR (CDCl , 500 MHz): δ 7.66 (s, 2H), 3.27 (m 4H), 3.03 (m,
3
1
3
1
4H), 1.50-1.00 (m, 48H), 0.799 (m, 12H) ppm; C NMR
H
16
O
2
(CDCl , 125 MHz): δ 167.30, 136.62, 136.03, 107.48, 49.10,
3
3
45.13, 31.82, 31.75, 29.42, 29.28, 29.08, 28.44, 27.35, 27.12,
26.59, 22.60, 14.08 ppm; HRMS calcd for C H I N O (M +
(
4
0
71
2
2
2
hexamethyldisilizane (0.75 mL of a 1.0 M solution in THF)
was syringed into a solution of (chloromethyl)triphenylphos-
phonium chloride (0.279 g, 0.805 mmol) in THF (4 mL), which
had been cooled in a dry ice/acetone bath. The dry ice bath
was then removed, and the reaction was stirred for 30 min
while warming to room temperature. A slurry of (+)-11 (0.103
g, 0.268 mmol) in dry THF was added to the reaction under a
stream of argon. After refluxing for 1 h, the mixture was
cooled to room temperature and directly filtered through a
short plug of silica gel (2 in. × 1 in., eluting with ca. 150 mL
of 30% ethyl acetate/hexane). The solvent was removed under
reduced pressure and the yellow solid triturated with hexane
and dried in vacuo, yielding 0.113 g (94%) of chloro-olefins (+)-
1) 865.3605, found 865.3602.
P r ep a r a tion of P olym er 4. Compound 2 (0.060 g, 0.069
mmol, 1.60 mL of a 0.0433M solution in toluene), toluene (2
mL), and diisopropylamine (1.5 mL) were sequentially added
to a flask containing (+)-1 (0.025 g, 0.066 mmol), Pd(PPh
0.004 g, 0.0034 mmol), and CuI (0.001 g, 0.0052 mmol). After
the mixture was heated at 70 °C for 4 h, it was cooled to room
temperature, and water and CH Cl were added. Washing
twice with HCl (1 M) and once with water, drying (MgSO ),
3 4
)
(
2
2
4
solvent removal, trituration with methanol and then with
hexane, and drying in vacuo gave 0.062 g (95%) of polymer 4,
a yellow solid. [R]
D
+3580 (c ) 0.180, CH
2
Cl
851, 1633, 1464, 1428 cm ; H NMR (CDCl
.10-7.10 (m, 16H), 3.80-2.70 (m, 8H), 1.60-0.60(m, 60H)
2
); IR(KBr): 2922,
-1
1
2
8
3
, 500 MHz): δ
1
1a , a mixture of cis/trans isomers, mp > 220 °C. [R]
D
+4870
1
(c 0.011, CH
2
Cl
00 MHz): δ 8.04-7.12 (m, 14H), 6.24-5.81 (m, 4H); C NMR
, 75 MHz): δ 133.21, 132.83, 131.73, 131.55, 131.47,
2
); IR(KBr): 3046, 3014, 1597; H NMR (CDCl
3
,
13
ppm; C NMR (CDCl
3
, 75 MHz): δ 168.32, 139.35, 136.0-
26.0 (m), 123.74, 120.09, 118.82, 118.65, 95.16, 85.55, 48.0-
7.2, 45.2-44.0, 32.21, 31.65, 30.35-28.50 (m), 28.19, 27.42,
7.06, 26.55, 22.52, 14.03 ppm. Anal. Calcd for C320
1
3
4
1
4
2
(CDCl
3
1
1
4
29.49-126.49 (m), 125.45, 123.80, 123.56, 118.18, 118.02,
H
406 10
N -
16.75 ppm; HRMS calcd for C30
48.0809.
H
18Cl
2
448.0786, found
37
O
10
I
2
:
C, 80.0; H, 8.5; N, 2.9. Found: C, 80.2; H, 8.1; N, 2.5.
P r ep a r a tion of Cyclop h a n es 5 a n d Isola tion of 5a .
Compound 3 (0.023 g, 0.027 mmol, 0.85 mL of a 0.064 M
solution in toluene), toluene (1.2 mL) and diisopropylamine
(
+)-2,15-Dieth yn yl[6]h elicen e (1). Methyllithium (2.6
mL of a 1.4 M solution in Et O) was syringed into a solution
2
of (+)-11a (0.104 g, 0.232 mmol) in THF (6 mL) which had
been cooled in a dry ice/acetone bath. After the mixture had
stirred at -78 °C for 1 h, the dry ice bath was removed, and
stirring was continued for 1.25 h while warming to room
temperature. Cautious addition of water (30 mL), followed
by two extractions with CH Cl (50 mL), drying (Na SO ),
2 2 2 4
solvent removal, chromatography (20% EtOAc in hexane), and
in vacuo drying yielded 0.087 g (100%) of pure (+)-1, a yellow
(
0.8 mL) were sequentially added to a flask containing (+)-1
(0.010 g, 0.027 mmol), Pd(PPh (0.003 g, 0.003 mmol), and
3 4
)
CuI (0.0007 g, 0.004 mmol). After the mixture was heated at
0 °C for 5 h 15 min, water and CH Cl were added. Washing
twice with HCl (1 M), once with sat. NaHCO , and once with
water, drying (Na SO ), and solvent removal gave a solid that
was triturated with methanol until the filtrate was clear. This
solid was dried, dissolved in CH Cl , and loaded onto a short
column of silica gel (3 in. m~ 0.5 in.). The column was first
washed with hexane and CH Cl . Subsequent elution with 1:1
CH Cl :acetone gave 0.023 g (88%) of crude cyclophanes 5, a
yellow solid. IR(KBr): 2924, 2854, 1732, 1639, 1465, 1435
9
2
2
3
2
4
2
2
solid, mp > 220 °C. [R]
D
+5140 (c 0.19, CH
2
Cl
, 400 MHz): δ 8.03 (d,
H, J ) 8.2 Hz), 7.99 (d, 2H, J ) 8.7 Hz), 7.97 (d, 2H, J ) 8.8
2
); IR(KBr):
2
2
208, 3038, 2102 cm-1; 1H NMR (CDCl
3
2
2
2
2
Hz), 7.92 (d, 2H, J ) 8.4 Hz), 7.79 (d, 2H, J ) 8.1 Hz), 7.72 (s,
2
(
1
H), 7.34 (d, 2H, J ) 8.2 Hz), 2.71 (s, 2H) ppm; 13C NMR
CDCl , 75 MHz): δ 133.22, 132.04, 131.85, 131.66, 129.02,
28.53, 127.75-127.13, 123.80, 118.24, 83.64, 76.14 ppm;
16 376.1252, found 376.1264.
-1
1
cm ; H NMR (CDCl
.8 (m, 8H), 1.8-0.7 (m, 60H) ppm; C NMR (CDCl
MHz): δ 168.86, 136.0-123.0 (m), 119.01, 117.90, 95.66, 86.10,
3
, 500 MHz): δ 8.2-6.0 (m, 16H), 3.6-
3
13
2
3
, 125
HRMS calcd for C30
H
5
0.32-48.48 (m), 46.11-44.14 (m), 34.0-26.0 (m), 23.48-21.90
m), 14.76-13.61 (m) ppm. Anal. Calcd for (C70 : C,
5.3; H, 8.5; N, 2.8. Found: C, 82.7; H, 8.3; N, 2.2. Two
P r ep a r a tion of o-Iod o-N,N-d ioctylben za m id e. Diocty-
lamine (2.16 g, 2.71 mL, 8.97 mmol) was added to a stirring
(
84 2 2 n
H N O )
8
solution of o-iodobenzoyl chloride (0.956 g, 3.59 mmol) in CH
Cl (20 mL) and refluxed overnight. After cooling to room
temperature, washing twice with HCl (1 M), once with water,
once with sat. NaHCO , once again with water, and drying
MgSO ), the solvent was removed under reduced pressure.
Chromatography (eluting with 5% acetone in CH Cl ) yielded
.57 g (89%) of a clear oil. IR(neat): 2927, 2855, 1641, 1458,
2
-
successive preparative silica gel TLC’s (the first was developed
with 0.5% EtOAc/CH Cl , the second with 1.5% EtOAc/
benzene) of a 10 mg sample of crude 5, followed by HPLC
2
2
2
3
(
4
(
(
36) Boden, E. P.; Keck, G. E. J . Org. Chem. 1985, 50, 2394.
37) The CHN analysis was compared to that of 4d (C320
MW ) 4806.6 Da), which falls near the lower limit of the estimated
MW of the polymer. The calculated value for 4e (C390 , MW
2
2
406 10 10 2
H N O I ,
1
1
-
1 1
424 cm ; H NMR (CDCl , 400 MHz): δ 7.81 (d, 1H, J ) 8.0
3
H
490 12 12 2
N O I
Hz), 7.36 (dd, 1H, J ) 7.6, 7.6 Hz), 7.19 (d, 1H, J ) 7.6 Hz),
7
) 5792.0 Da), the MW of which is near the upper limit of the estimated
MW of the polymer, is: C, 80.9; H, 8.5; N, 2.9.
.04 (dd, 1H, J ) 7.7, 7.7), 3.76 (m, 1H), 3.22 (m, 1H), 3.04