+
ꢃ
1
Yield 120 mg (165 mmol, 46%), mp 134–137 C. H NMR (400
7
0 eV): calcd m/z for ([M ꢂ Br] ) 360.986, found 360.987 (100%),
+
ꢃ
calcd m/z for ([M]c ) 441.903, found 441.904 (54%).
MHz, CDCl , 25 C): d 7.43 (d, J ¼ 7.6 Hz, 2H), 7.14 (dd, J ¼ 7.8
3
Hz, J ¼ 1.0 Hz, 2H), 6.94 (dd, J ¼ 7.6 Hz, J ¼ 7.6 Hz, 2H), 6.51
(s, 2H), 6.39 (s, 2H), 3.92 (t, J ¼ 6.2 Hz, 4H), 3.30 (s, 2H), 1.83
(
±)-1,6-Dibromo-11,14-ditetradecyloxytriptycene (±)-4
(
13
m, 4H), 1.55 (m, 4H), 1.4–1.2 (m, 40H), 0.88 (t, J ¼ 7.0 Hz, 6H).
Iptycene quinone (ꢀ)-2 (3.5 g, 7.92 mmol) was dissolved in
a mixture of AcOH (35 mL) and THF (105 mL). Zinc dust (7 g)
was added and the mixture was stirred at rt for 2 h. After
filtration of the mixture through a pad of silica gel using MeOH
as solvent, the yellow filtrate was poured into water (500 mL) and
the formed white solid was filtered, washed with water, and dried
in vacuo. This material, K CO (3.74 g, 27 mmol), and KI (900
ꢃ
3
, 25 C): d 149.0, 148.2, 145.8, 135.0,
C NMR (100 MHz, CDCl
28.9, 125.0, 124.9, 117.7, 111.5, 81.6, 80.1, 70.1, 45.6, 32.1, 29.9
1
(
6ꢁ), 29.8, 29.7, 29.6, 26.3, 22.9, 14.3. HRMS (DART, pos.
+
([M + H] ) 727.545, found
mode): calcd m/z for C52
H
70
O
2
7
27.546.
2
3
Polymer P1
mg, 5.4 mmol) were suspended in 2-butanone (20 mL) and
C H Br (8.0 mL, 27 mmol) was added. The mixture was
1
4
29
Diyne (ꢀ)-5 (59.0 mg, 106 mmol), diiodide 6 (77.4 mg, 106 mmol),
Pd(PPh ) (5.78 mg, 5 mmol), and CuI (0.95 mg, 5.0 mmol) were
placed in a flame-dried Schlenk tube. The tube was transferred
refluxed for 22 h. After cooling to rt the mixture was poured into
3
4
water (30 mL) and extracted with diethyl ether (2 ꢁ 50 mL). The
combined organic phases were washed with HCl (0.05 M), H
2
O,
into a glove box and toluene (1.75 mL) and i-Pr NH (0.75 mL)
2
and brine and dried over MgSO
the residue was subjected to column chromatography (SiO
CH Cl
/n-hexane ¼ 1 : 9) and recrystallized from THF/acetone
to yield a colorless powder. Yield 3.90 g (4.66 mmol, 59%), mp
4
. After removal of the solvent
were added. The tube was sealed and the mixture was heated to
ꢃ
2
,
4 3
60 C for 24 h. Sat. NH Cl solution and CHCl were added and
2
2
the org. phase was separated. After washing the org. phase with
sat. NH Cl solution (2ꢁ), H O and brine it was dried over
4
2
ꢃ
1
ꢃ
1
59 C. H NMR (400 MHz, CDCl
3
, 25 C): d 7.37 (d, J ¼ 7.2
MgSO . After filtration the solvent was removed and the residue
4
Hz, 2H), 7.18 (dd, J ¼ 8.2 Hz, J ¼ 0.8 Hz, 2H), 6.85 (dd, J ¼ 8.0
Hz, J ¼ 7.6 Hz, 2H), 6.52 (s, 2H), 6.35 (s, 2H), 3.93 (t, J ¼ 6.7 Hz,
taken up in CHCl . Precipitation by slow addition to MeOH and
3
1
filtration yielded the polymer. Yield 90 mg (88 mmol, 83%). H
ꢃ
4
H), 1.84 (m, 4H), 1.55 (m, 4H), 1.4–1.2 (m, 40H), 0.88 (t, J ¼ 7.0
NMR (400 MHz, CDCl , 25 C): d 7.6–7.3 (br m, 4H), 7.23 (br
3
13
ꢃ
Hz, 6H). C NMR (100 MHz, CDCl , 25 C): d 148.9, 147.6,
3
m, 2H), 7.00 (br m, 2H), 6.6–6.4 (br m, 4H), 3.95 (br m, 4H), 3.1–
2.6 (br m, 4H), 1.93 (br m, 2H), 1.78 (br m, 4H), 1.5–1.1 (br m,
1
3
45.3, 134.5, 129.1, 126.8, 123.5, 119.4, 111.3, 69.9, 47.4, 32.1,
0.0–29.9 (6ꢁ), 29.8, 29.7, 29.6, 26.4, 22.9, 14.3. HRMS (EI, 70
60H), 1.0–0.7 (br m, 18H). GPC (THF, polystyrene): M ¼ 1.9 ꢁ
n
+
29] ) 443.918, found 443.918
4
eV): calcd m/z for ([M ꢂ 2C14
H
10 Da, M /M ¼ 2.4.
w
n
+
H29] ) 640.137, found 640.138
(
100%), calcd m/z for ([M ꢂ C14
+
(
15%), calcd m/z for ([M]c ) 836.358, found 836.356 (10%).
Acknowledgements
This work was supported by the National Science Foundation
and A.L. thanks the Alexander-von-Humboldt Foundation for
a Feodor-Lynen fellowship. We are grateful to Merck KGaA for
supplying the liquid crystals used in these investigations.
(
±)-6,11-Diethynyl-1,4-ditetradecyloxytriptycene (±)-5
Dibromide (ꢀ)-4 (300 mg, 358 mmol), Pd(PhCN) Cl (9.90 mg,
2
2
2
5.8 mmol), (t-Bu PH)BF (16.2 mg, 55.9 mmol), and CuI (3.28
3 4
mg, 17.2 mmol) were placed in an oven-dried Schlenk tube.
Subsequently, the tube was evacuated and refilled with argon
References
(
2
5 cycles). THF (1.5 mL) and i-Pr NH (144 mL, 1.03 mmol) were
added through a septum and the mixture was stirred at rt for 15
min. Trimethylsilylacetylene (145 mL, 1.03 mmol) was added and
the septum replaced by a glass stopper. The mixture was heated
1 (a) D.-K. Yang and S.-T. Wu, Fundamentals of Liquid Crystal Devices,
Wiley, Chichester, 2006; (b) Handbook of Liquid Crystals, ed.
D. Demus, J. Goodby, G. W. Gray, H.-W. Spiess and V. Vill, Wiley-
VCH, Weinheim, 1998, vol. 1; (c) P. J. Collings and M. Hird,
Introduction to Liquid Crystals: Chemistry and Physics, Taylor &
Francis, London, 1997.
ꢃ
to 50 C for 70 h and additional 100 mL portions of trime-
thylsilylacetylene were added every 24 h. The solvent was evap-
2
3
I. Dierking, Adv. Mater., 2000, 12, 167–181.
2
orated in vacuo and the residue was chromatographed (SiO ,
(a) P. Mariani, B. Samori, A. S. Angeloni and P. Ferruti, Liq. Cryst.,
1986, 1, 327–336; (b) D.-K. Yang, L.-C. Chien and J. W. Doane,
Appl. Phys. Lett., 1992, 60, 3102–3104.
CH Cl /n-hexane ¼ 2 : 8). After evaporation of the solvent, the
2
2
residue was taken up in a mixture of THF (3 mL) and MeOH (1.5
mL), and K CO (180 mg, 1.30 mmol) was added. The mixture
4
5
T. M. Swager, Acc. Chem. Res., 2008, 41, 1181–1189.
(a) T. M. Long and T. M. Swager, Adv. Mater., 2001, 13, 601–604; (b)
T. M. Long and T. M. Swager, J. Am. Chem. Soc., 2002, 14, 3826–
3827.
2
3
was stirred for 2 h at rt and diluted with diethyl ether and water.
The aqueous phase was separated and extracted with Et O. The
combined org. phases were washed with HOAc (10%), water and
brine and dried over MgSO . Column chromatography (SiO
CH Cl
/n-hexane ¼ 2 : 8 and hexanes/EtOAc ¼ 98 : 2) and
recrystallization from EtOH yielded (ꢀ)-4 as colorless powder.
2
6
(a) Z. Zhu and T. M. Swager, J. Am. Chem. Soc., 2002, 124, 9670–9671;
(
b) J. Hoogboom and T. M. Swager, J. Am. Chem. Soc., 2006, 128,
4
2
,
1
5058–15059; (c) A. Ohira and T. M. Swager, Macromolecules, 2007,
0, 19–25.
7 R. A. M. Hikmet, Liq. Cryst., 1991, 9, 405–416.
2
2
4
This journal is ª The Royal Society of Chemistry 2010
J. Mater. Chem., 2010, 20, 8107–8111 | 8111