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3H), 1.23–1.51 (m, 10H), 1.79 (m, 2H), 4.03 (t, 2H), 6.96 (q, 4H),
7.85 ppm (q, 4H).
(yield: 0.24 g, 60%). 1H NMR (400 MHz, CDCl3, TMS): d=0.89 (t,
18H), 1.23–1.51 (m, 60H), 1.80 (m, 12H), 3.77 (t, 24H), 3.89 (m,
24H), 4.02 (t, 12H), 4.19 (m, 28H), 4.64 (d, 1H), 5.01 (t, 1H), 5.36 (q,
1H), 5.44 (d, 1H), 6.99 (q, 24H), 7.24 (s, 2H), 7.31 (s, 2H), 7.83 ppm
(q, 24H); 13C NMR (400 MHz, CDCl3, TMS): d=161.2, 160.6, 152.4,
147.1, 146.8, 124.3, 124.2, 114.7, 109.2, 72.5, 70.8, 70.6, 70.5, 69.6,
68.9, 68.3, 67.6, 31.7, 29.2, 26.0, 22.6, 14.1 ppm; MS (MALDI-TOF):
m/z calcd: 3093.69 [M+K]+; found: 3131.6; elemental analysis
calcd (%) for C176H234N12O36: C 68.33, H 7.62, N 5.43, O 18.62; found:
C 67.76, H 7.329, N 5.371.
2-(2-{2-(4-((4-(Octyloxy-
(phenyl)diazenyl)phenoxy)ethoxy}ethoxy)-ethanol (4): A solution
of 3 (4 g, 12.25 mmol), TEO (8.26 g, 49 mmol), and K2CO3 (6.77 g,
49 mmol) in dried DMF (100 mL) was heated at reflux for 24 h.
After the reaction, the solvent was removed in vacuum and re-
maining residue was dissolved in ethyl acetate and extracted with
distilled water several times. The organic layer was dried over
MgSO4. The purified product by recrystallization in MeOH was a yel-
1
lowish crystal (Yield: 67%, 3.91 g). H NMR (400 MHz, CDCl3, TMS):
d=0.89 (t, 3H), 1.23–1.51 (m, 10H), 1.80 (m, 2H), 3.64 (t, 4H), 3.74
(m, 4H), 3.89 (t, 2H), 4.02 (t, 2H), 4.21 (t, 2H), 7.01 (q, 4H),
7.86 ppm (d, 4H).
Acknowledgements
This work was mainly supported by the Human Resource Train-
ing Project for Regional Innovation, Basic Science Research Pro-
gram (2013R1A1A2007238), Converging Research Center Pro-
gram (2013K001428) and BK21Plus Program, Korea. D.Y.K. ap-
preciates the support from Global Ph.D Fellowship Program
(2013H1A2A1033907) and K.U.J. acknowledges the support
from LG Yonam Foundation.
2-(2-{2-(4-((4-(Octyloxy)phenyl)diazenyl)phenoxy)ethoxy}e-
thoxy)-ethyl 4-toluenesulfonate (5): A solution of compound 4
(3.5 g, 7.63 mmol), tosyl chloride (5.82 g, 30.53 mmol), and triethyl-
amine (TEA; 7.72 g, 76.34 mmol) in dried CH2Cl2 (60 mL) was
heated at reflux for 1 h. After the reaction, solvent was removed in
vacuum and remaining residue was re-dissolved in CH2Cl2 and
washed with distilled water three times. It was purified by column
chromatography with silica gel by using ethyl acetate/n-hexane=
1:1, and recrystallization with MeOH. The resulting product was
a yellowish solid (Yield: 88%, 4.11 g). 1H NMR (400 MHz, CDCl3,
TMS): d=0.89 (t, 3H), 1.23–1.51 (m, 10H), 1.80 (m, 2H), 2.43 (s,
3H), 3.64 (t, 2H), 3.74 (m, 4H), 3.89 (t, 2H), 4.02 (t, 2H), 4.21 (t, 4H),
6.99 (q, 4H), 7.34 (d, 2H), 7.70 (d, 2H), 7.86 ppm (d, 4H).
Keywords: chirality · dendrimers · liquid crystals · phase
transitions · photochromism
Ed. 1999, 38, 884; b) V. Percec, M. R. Imam, T. K. Bera, V. S. K. Balagurusa-
3,4,5-Tris[2-(2-{2-(4-((4-(octyloxy)phenyl)diazenyl)phenoxy)-
ethoxy}ethoxy)-ethoxy]benzoic acid methyl ester (6): A solution
of 5 (1.89 g, 3.1 mmol), methyl gallate (0.14 g, 0.77 mmol), and
K2CO3 (0.64 g, 4.63 mmol) in dried DMF (20 mL) was heated at
reflux at 908C for 3 days under a nitrogen atmosphere. After the
reaction, the solvent was removed in vacuum and remaining resi-
due was dissolved in CHCl3 and washed with distilled water. After
drying the organic layer over MgSO4, it was purified by column
chromatography with silica gel using THF/CH2Cl2 =1:7. The result-
ing product was yellowish powder (Yield: 63%, 0.74 g). 1H NMR
(400 MHz, CDCl3, TMS): d=0.89 (t, 9H), 1.23–1.51 (m, 30H), 1.80
(m, 6H), 3.76 (t, 12H), 3.88 (m, 15H), 4.02 (t, 6H), 4.18 (m, 12H),
6.99 (q, 12H), 7.29 (s, 2H), 7.84 ppm (m, 12H).
12, 224; b) G.-C. Kuang, Y. Ji, X.-R. Jia, Y. Li, E.-Q. Chen, Y. Wei, Chem.
khomlinova, L. Su, B. Taheri, T. J. White, T. J. Bunning, Nature 2012, 485,
2008, 29, 193; b) R. Cervera-Procas, C. Sanchez-Somolinos, R. L. Serrano,
689; e) A. Archut, R. Vogtle, L. D. Colar, G. C. Azzellini, V. Balzani, P. S.
Kim, M. Lee, H. K. Bisoyi, Q. Li, H. Maeda, Y. Li, Y. Zhang, H. Yu, A. Khabi-
bullin, I. Zharov, C. Xue, A. Kawamura, T. Miyat, R. Yoshida, A. Pranzetti,
J. A. Preece, P. M. Mendes, A. Malhotra, M. Mclnnis, J. Anderson, L. Zhai,
Intelligent Stimuli Responsive Materials: From Well-defined Nanostructures
to Applications (Ed.: Q. Li), Wiley, Hoboken, 2013; g) H. Takezoe, C. Xue,
Q. Li, R. Tamura, Y. Uchida, K. Suzuki, Y. Zhang, J. Etxebarria, C. V. Yela-
maggad, S. K. Pradas, Y. Wang, J. P. F. Lagerwall, X. Tong, Y. Zhao, M.
O’Neill, S. M. Kelly, G. Scallia, A. M. Urbas, D. P. Brown, Y. Reznikov, B. R.
Acharya, S. Kumar, H.-S. Park, O. D. Lavrentovich, J. T. Hunter, N. L.
Abbott, D.-K. Yang, T. D. Wilkinson, R. Rajesekharan, Liquid Crystals
Beyond Displays: Chemistry, Physics, and Applications (Ed.: Q. Li), Wiley,
Hoboken, 2012.
3,4,5-Tris[2-(2-{2-(4-((4-(octyloxy)phenyl)diazenyl)phenoxy)-
ethoxy}-ethoxy)ethoxy]benzoic acid (7): Aqueous NaOH (10m,
3.7 mL) was added to a stirred solution of 6 (0.6 g, 0.4 mmol) in
THF/MeOH (10/8 mL). The mixture was heated at reflux for 3 h,
and then neutralized with an HCl to obtain a precipitate. The pre-
cipitate was filtered off and washed with water. The crude product
was purified by reprecipitation from CHCl3 and EtOH, and dried
under vacuum to afford 7 as a waxy yellow solid (yield: 94%,
1
0.56 g). H NMR (400 MHz, CDCl3, TMS): d=0.89 (t, 9H), 1.23–1.51
(m, 30H), 1.80 (m, 6H), 3.76 (t, 12H), 3.88 (m, 12H), 4.02 (t, 6H),
4.18 (m, 12H), 6.99 (q, 12H), 7.29 (s, 2H), 7.84 ppm (m, 12H).
AZ3DLC (8): N,N’-Dicyclohexylcarbodiimide (DCC; 0.77 g,
3.75 mmol)
and
4-dimethylaminopyridine
(DMAP;
1.8 g,
14.75 mmol) were added to a solution of 7 (0.6 g, 0.4 mmol) in
CH2Cl2/THF (5 mL/1 mL). After stirring at room temperature for
20 min, isosorbide (0.019 g, 0.13 mmol) was added as a solid, and
the solution was sonicated in an ultrasound bath until a clear solu-
tion was obtained. The solution was stirred for 72 h at room tem-
perature. After the reaction, distilled water was added and the
product was extracted with CHCl3. The combined organic layer was
dried over anhydrous MgSO4. After filtration and evaporation, the
crude product was purified by column chromatography with silica
gel using ethyl acetate/CHCl3 =3:1 to yield 8 as a yellow powder
&
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Chem. Eur. J. 2014, 20, 1 – 8
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