Template Polymerization of Columnar Liquid Crystals
FULL PAPER
(
15 wt%, 2.5 mL), and water (7.5 mL) were successively added dropwise
Acknowledgements
to the resultant mixture. The suspension formed was separated by filtra-
tion, and the solid was extracted with THF (100 mL) by using a Soxhlet
extractor. The filtrate and the extract were combined and concentrated
under reduced pressure. The remaining white solid was crystallized from
ethanol/hexane (1:3, v/v; 20 mL) to yield rac-14 (3.35 g, 17.9 mmol,
7
1
6
We acknowledge Dr. Toshimi Shimizu and Dr. Hiroyuki Minamikawa
National Institute of Advanced Industrial Science and Technology) for
(
XRD measurements. We would like to thank Professor Takuzo Aida and
Professor Takashi Kato (The University of Tokyo) for use of the POM
and DSC equipment. A part of this work was financially supported by a
Grants-in-Aid for Exploratory Research (No. 16655043) from the Minis-
try of Education, Culture, Sports, Science, and Technology (Japan), the
Ogasawara Science and Technology Fund, the Circle for the Promotion
of Science and Engineering, and the Association for the Progress of New
Chemistry.
[
18b]
0%). M.p. 116–1188C (lit.
1188C); FTIR (KBr): n˜ =3388, 3054, 1599,
477, 1422, 1382, 1332, 1163, 1121, 1071, 1015, 948, 897, 860, 822, 739,
ꢀ
1
1
55, 617, 482cm
=7.6 Hz, 1H), 3.11 (dd, J
=3.9 Hz, 1H), 7.46 (m, 3H), 7.83 ppm (m, 4H); C NMR (75 MHz,
]DMSO): d=49.89, 74.35, 124.25, 124.68, 125.48, 125.96, 127.44,
27.49, 127.72, 132.28, 132.81, 141.93 ppm.
;
H NMR (300 MHz, CDCl
3
): d=2.90 (dd, J
1
=12.9,
J
J
2
1
=12.9, J =3.9 Hz, 1H), 4.81 (dd, J
2
1
=7.6,
1
3
2
[
D
6
1
Synthesis of R-enriched 2-amino-1-(2-naphthyl)ethanol (14) and determi-
nation of chiral HPLC elution order: R-enriched 2-amino-1-(2-naphthyl)-
ethanol was synthesized from enantiopure (R)-2-naphthylglycolic acid via
[
1] a) T. Kato, N. Mizoshita, K. Kishimoto, Angew. Chem. 2006, 118,
4–74; Angew. Chem. Int. Ed. 2006, 45, 38–68; b) I. M. Saez, J. W.
Goodby, J. Mater. Chem. 2005, 15, 26–40; c) D. T. Bong, T. D. Clark,
J. R. Granja, M. R. Ghadiri, Angew. Chem. 2001, 113, 1016–1041;
Angew. Chem. Int. Ed. 2001, 40, 988–1011; d) C. Tschierske, J.
Mater. Chem. 2001, 11, 2647–2671; e) D. W. Bruce, Acc. Chem. Res.
4
2
,2-dimethyl-5-(2-naphtyl)-1,3-dioxolan-4-one according to the methods
[
19]
described in the literature with some modifications (78% ee). By com-
paring the HPLC profile of the R-enriched sample thus obtained with
that of the racemic one, the chiral HPLC elution order of the enantio-
mers was unambiguously determined. Retention time: (R)-14, 104 min;
2
000, 33, 831–840; f) V. Percec, J. Heck, G. Johansson, D. Tomazos,
M. Kawasumi, P. Chu, G. Ungar, Mol. Cryst. Liq. Cryst. 1994, 254,
37–196.
(
(
S)-14, 118 min. (HPLC conditions: eluent, methanol/aqueous HClO
pH 2.0)=15:85, v/v; flow rate, 0.60 mLmin ).
4
ꢀ
1
1
General procedure for the preparation of the salt of 1 with a 2-amino al-
cohol: diethyl ether solution (1.0 mL) of 2-amino alcohol
1.00 mmol) was added to diethyl ether solution (10 mL) of
843.2mg, 1.00 mmol), and the resultant solution was stirred at room
[2] a) J. Jin, V. Nguyen, W. Gu, X. Lu, B. J. Elliott, D. L. Gin, Chem.
Mater. 2005, 17, 224–226; b) M. Zhou, T. J. Kidd, R. D. Noble, D. L.
Gin, Adv. Mater. 2005, 17, 1850–1853; c) U. Beginn, G. Zipp, A.
Mourran, P. Walther, M. Mçller, Adv. Mater. 2000, 12, 513–516.
[3] a) J. B. Beil, S. C. Zimmerman, Chem. Commun. 2004, 488–489;
b) S. C. Zimmerman, I. Zharov, M. S. Wendland, N. A. Rakow, K. S.
Suslick, J. Am. Chem. Soc. 2003, 125, 13504–13518; c) E. Mertz,
S. C. Zimmerman, J. Am. Chem. Soc. 2003, 125, 3424–3425.
A
a
(
(
a
1
temperature for 3 min. The solvent was removed by an argon flow and fi-
nally by evaporation under reduced pressure. The molar ratio of 1 to the
1
amine in the resultant residue was confirmed by H NMR spectroscopy.
Salt 1·
A
C
H
T
R
E
U
N
G
(1R,2S)-5: FTIR (KBr): 3440, 3230, 3030, 2920, 2852, 1721, 1637,
1
1
621, 1579, 1541, 1520, 1501, 1472, 1409, 1396, 1375, 1295, 1275, 1197,
[4] a) L. Y. Jin, J. Bae, J.-H. Ryu, M. Lee, Angew. Chem. 2006, 118,
666–669; Angew. Chem. Int. Ed. 2006, 45, 650–653; b) C. S. Peci-
novsky, G. D. Nicodemus, D. L. Gin, Chem. Mater. 2005, 17, 4889–
4891; c) Y. Xu, W. Gu, D. L. Gin, J. Am. Chem. Soc. 2004, 126,
1616–1617; d) W. Gu, W.-J. Zhou, D. L. Gin, Chem. Mater. 2001, 13,
1949–1951; e) S. A. Miller, E. Kim, D. H. Gray, D. L. Gin, Angew.
Chem. 1999, 111, 3205–3210; Angew. Chem. Int. Ed. 1999, 38, 3022–
ꢀ
1
1
120, 1058, 979, 811, 780, 743, 721, 700, 660 cm
): d=1.10–1.90 (m, 57H), 3.32(m, 1H), 3.51 (dd, 1H), 3.73 (dd,
H), 4.00 (t, J=6.6 Hz, 6H), 4.10–4.20 (m, 6H), 5.00 (br, 1H+1H+
H), 5.80 (d, J=10.2Hz, 3H), 6.15 (dd, =10.5, J =17.3 Hz, 3H),
.40 ppm (d2, J =17.3, 15.9 Hz, 3H+1H).
; H NMR (300 MHz,
CDCl
3
1
2
6
J
1
2
1
General procedure for the g-ray-induced polymerization of the salt of 1
with a 2-amino alcohol: A diethyl ether solution (10 mL) of 1 (843 mg,
1
glass tubes (length 100 mm, diameter 20 mm), and the solvent was re-
moved by an argon flow and subsequent evaporation under reduced pres-
sure at room temperature to afford the LC salt. The glass tubes were
3
026.
5] a) Y. Ishida, S. Amano, N. Iwahashi, K. Saigo, J. Am. Chem. Soc.
006, 128, 13068–13069; b) Y. Ishida, S. Amano, K. Saigo, Chem.
[
.00 mmol) and a 2-amino alcohol (1.00 mmol) was partitioned into three
2
Commun. 2003, 2338–2339; c) H.-K. Lee, H. Lee, Y. H. Ko, Y. J.
Chang, N.-K. Oh, W.-C. Zin, K. Kim, Angew. Chem. 2001, 113,
2741–2743; Angew. Chem. Int. Ed. 2001, 40, 2669–2671.
6
0
evacuated, sealed, and applied to a Co g-ray irradiator (dose rate,
ꢀ
1
[6] a) S. Oshita, A. Matsumoto, Chem. Eur. J. 2006, 12, 2139–2146;
b) A. Matsumoto, D. Fujioka, T. Kunisue, Polym. J. 2003, 35, 652–
1
.7 kGyh ; irradiation time, 48 h at room temperature). The irradiated
samples were detached from the glass tubes, combined, mechanically
ground, washed with CHCl (20 mL), and collected by filtration (Advan-
6
2
61; c) A. Matsumoto, S. Oshita, D. Fujioka, J. Am. Chem. Soc.
002, 124, 13749–13756.
3
tec T050A047A PTFE membrane filter, 0.5 mm mesh). The resultant
white powder was dried in vacuo to give the cross-linked polymer.
[
[
[
7] a) A. G. Mayes, M. J. Whitcombe, Adv. Drug Delivery Rev. 2005, 57,
1
2
742–1778; b) K. Haupt, K. Mosbach, Chem. Rev. 2000, 100, 2495–
504; c) G. Wulff, Angew. Chem. 1995, 107, 1958–1979; Angew.
General procedure for the guest-exchange reaction of the cross-linked
polymer: The cross-linked polymer (45.0 mg) was loaded into a centri-
fuge tube, and a methanol solution (18 mm, 5.0 mL) of an amine was
added. The resultant mixture was left to stand at 308C for 96 h and cen-
trifuged (3000 rpm, 3 min). The amounts of the template amine and the
guest amine in the supernatant were estimated by HPLC.
Chem. Int. Ed. Engl. 1995, 34, 1812–1832.
8] a) D. Gin, K. Yonezawa, Synth. Met. 2001, 121, 1291–1294; b) H.
Deng, D. L. Gin, R. C. Smith, J. Am. Chem. Soc. 1998, 120, 3522–
3
1
523; c) R. C. Smith, W. M. Fischer, D. L. Gin, J. Am. Chem. Soc.
997, 119, 4092–4093.
General procedure for the extraction of the guest amine from the cross-
linked polymer: The guest-exchange reaction was conducted in the same
manner as described above. The cross-linked polymer was recovered by
centrifugation (3000 rpm, 3 min) and suspended in a methanol solution
9] As described in our previous report (reference [5b]), the salts of an
unpolymerizable analogue of 1 with simple primary amines did not
display any LC phases, implying that the existence of a hydroxyl
group was essential for the formation of a stable LC structure. On
the basis of this result, only 2-amino alcohols were used as the base
part of salts in this study.
(
1.0m, 5.0 mL) of 2-aminoethanol. The resultant mixture was sonicated
for 2h and centrifuged (3000 rpm, 3 min), and the amount of the guest
amine extracted into the supernatant was estimated by HPLC.
[
10] Reflections observed for 1·(S)-3 on XRD measurement: d spacings
) calcd for Miller indices of (100), (110), (210), (300), and (001):
6.6, 21.2, 13.9, 12.2, and 3.9; found: 36.5, 21.2, 13.9, 12.2, and 3.9.
(
3
[
[
11] W. Hohn, B. Tieke, Macromol. Chem. Phys. 1996, 197, 821–831.
12] Our previous work (reference [5a]) showed that the presence of
vacant sites generated by the release of (1R,2S)-5 caused a signifi-
cant alteration of the whole system, and the original structural order
Chem. Eur. J. 2007, 13, 5186 – 5196
ꢀ 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5195