Macromolecules, Vol. 36, No. 26, 2003
Polybinaphthalenes 9741
J ) 4.4 Hz; 2H), 7.35 (d; 2H),7.29 (d; J ) 16.1 Hz; 2H), 7.25
(dd; 2H), 7.22 (d; 4H), 7.17 (d; J ) 4.4 Hz; 2H), 7.01 (d; J )
16.1 Hz; 2H), 6.95 (d; 2H), 6.30 (d; 4H), 4.08 (m; 12H), 3.32 (q;
4H), 2.65 (m; 4H), 1.30 (m; 12H), 0.78 (t; 6H). 13C NMR (CDCl3,
ppm): δ ) 162.6, 161.8, 161.2, 154.3, 150.7, 148.1, 147.9, 147.3,
135.2, 134.6, 132.4, 130.5, 129.9, 129.8, 128.8, 128.7, 126.9,
125.7, 123.4, 120.1, 117.8, 116.2, 116.0, 111.4, 108.1, 67.8, 49.0,
44.6, 37.4, 36.6, 13.5, 13.4, 11.6.
NaHCO3 solution and with brine and dried over MgSO4. After
evaporation of the solvent, the product was purified by column
chromatography (silica gel; eluent: dichloromethane/ethyl
acetate (95:5 v/v)) and isolated as a glass. Yield: 14.5 g (97%).
1H NMR (CDCl3, ppm): δ ) 8.60 (s; 1H), 7.75 (d; J ) 4.4 Hz;
1H), 7.41 (d; 2H), 7.35 (d; J ) 16.1 Hz; 1H), 7.17 (d; J ) 4.4
Hz; 1H), 7.04 (d; J ) 16.1 Hz; 1H), 6.65 (d; 2H), 4.10 (q +q;
4H), 3.63 (t; 2H), 3.42 (q; 2H), 3.32 (t; 2H), 1.60 (m; 2H), 1.2
(m; 6H), 1.30 (t + t; 6H), 1.22 (t; 3H), 0.92 (s; 9H), 0.07 (s;
6H). 13C NMR (CDCl3, ppm): δ ) 162.8, 161.8, 161.1, 150.7,
149.0, 148.1, 147.2, 135.1, 134.6, 129.0, 125.8, 124.1, 116.3,
112.2, 108.1, 62.8, 50.3, 45.0, 37.4, 36.6, 32.7, 27.6, 27.0, 25.7,
24.7, 17.3, 13.5, 13.4, 12.4, -4.6. MS: m/z ) 637 (M+), 436
(M+ - C11H25OSi).
25
b. m on -(2,h ). Yield: 1.28 g (43%); [R]D ) +1.1 × 104 deg
dm-1 mol-1 L (c ) 0.013 in THF). 1H NMR (CDCl3, ppm): δ )
8.58 (s; 1H), 7.99 (d + d; J ) 2.2 Hz; 2H), 7.82 (d + d; 2H),
7.74 (d; J ) 4.4 Hz; 1H), 7.35 (d + d; 2H), 7.30 (d; J ) 16.1
Hz; 1H), 7.25 (m; 4H), 7.17 (d; J ) 4.4 Hz; 1H), 7.00 (d; J )
16.1 Hz; 1H), 6.96 (d; 1H), 6.93 (d; 1H), 6.33 (d; 2H), 4.08 (m;
6H), 3.86 (m; 2H), 3.55 (q; 2H), 2.73 (t; 2H), 1.29 (m; 9H), 0.98
(m; 4H), 0.83 (m; 4H), 0.78 (t; 3H). 13C NMR (CDCl3, ppm):
δ ) 162.7, 161.8, 161.4, 154.7, 154.4, 150.7, 148.2, 147.9, 147.3,
135.4, 134.6, 132.5, 130.5, 130.2, 129.8, 129.6, 128.9, 128.6,
128.5, 127.1, 126.9, 125.7, 125.6, 123.3, 120.4, 119.6, 117.7,
117.3, 116.3, 116.2, 115.9, 111.4, 108.0, 69.5, 67.7, 49.1, 44.7,
37.3, 36.6, 31.2, 29.2, 25.3, 22.4, 13.9, 13.5, 13.4, 11.7.
Ack n ow led gm en t. We are very grateful to KVH
Industries, Inc., Middletown, RI, for their financial
support. This work was also supported by the Fund
for Scientific Research-Flanders (FWO-Vlaanderen;
G.0261.02, G. 0260.03), by the Katholieke Universiteit
Leuven (GOA/2000/03), and by the Belgian Government
(IUAP P5/03). G.K. and S.S. are doctoral fellows, and
T.V. is a postdoctoral fellow of the Fund for Scientific
Research-Flanders.
c. m on -(6,6). Yield: 1.58 g (36%); [R]D ) +1.0 × 104 deg
25
dm-1 mol-1 L (c ) 0.015 in THF). 1H NMR (CDCl3, ppm): δ )
8.59 (s; 2H), 7.97 (d; J ) 1.8 Hz; 2H), 7.81 (d; 2H), 7.75 (d;
J ) 4.0 Hz; 2H), 7.37 (d; 2H), 7.36 (d; J ) 13.9 Hz; 2H), 7.29
(dd; 2H), 7.22 (d; 4H), 7.16 (d; J ) 4.0 Hz; 2H), 7.04 (d; J )
13.9 Hz; 2H), 7.00 (d; 2H), 6.58 (d; 4H), 4.08 (m; 12H), 3.38 (q;
4H), 3.11 (t; 4H), 1.34 (qu; 4H), 1.28 (m; 12H), 1.17 (t; 6H),
0.98 (t + t; 12H). 13C NMR (CDCl3, ppm): δ ) 162.7, 161.8,
161.5, 154.7, 150.7, 148.7, 147.8, 147.3, 135.5, 134.5, 132.5,
130.2, 129.8, 129.5, 129.1, 128.5, 127.1, 125.6, 123.0, 120.0,
117.3, 116.4, 115.6, 111.6, 107.9, 69.4, 50.1, 45.0, 37.3, 36.6,
29.2, 27.3, 26.5, 25.6, 13.5, 13.4, 12.4.
Su p p or tin g In for m a tion Ava ila ble: A representative
UV-vis spectrum of a spin-coated film of p ol-(2,2)-0.25. This
material is available free of charge via the Internet at http://
pubs.acs.org.
Refer en ces a n d Notes
d . m on -(6,h ). Yield: 2.16 g (70%); [R]D ) +1.3 × 104 deg
25
(1) (a) Shi, Y.; Zhang, C.; Zhang, H.; Bechtel, J . H.; Dalton, L.
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Samyn, C. Polymer 2003, 44, 3785.
(7) Molina, P.; Vilaplana, M. J .; Pastor, A. Synthesis 1992, 827.
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dm-1 mol-1 L (c ) 0.011 in THF). 1H NMR (CDCl3, ppm): δ )
8.61 (s; 1H), 8.02 (d; J ) 1.8 Hz; 1H), 7.97 (d; J ) 2.2 Hz; 1H),
7.82 (d; 1H), 7.80 (d; 1H), 7.76 (d; J ) 4.0 Hz; 1H), 7.50 (d;
2H), 7.40 (d; 1H), 7.37 (d; J ) 16.8 Hz; 1H), 7.29 (m; 3H), 7.22
(d; J ) 4.0 Hz; 1H), 7.05 (d; J ) 16.8 Hz; 1H), 7.01 (dd; 1H),
6.99 (dd; 1H), 6.59 (d; 2H), 3.95 (m; 8H), 3.37 (q; 2H), 3.12 (t;
2H), 1.32 (m; 6H), 1.28 (t + t; 6H), 1.18 (t; 3H), 0.97 (m; 10H),
0.76 (t; 3H). 13C NMR (CDCl3, ppm): δ ) 162.7, 161.8, 161.6,
154.8, 154.6, 150.7, 148.8, 134.5, 132.6, 132.5, 130.2, 130.1,
129.7, 129.5, 129.4, 129.1, 128.4, 127.2, 127.1, 123.0, 120.0,
117.3, 117.2, 111.6, 107.9, 69.5, 69.4, 37.3, 31.3, 29.2, 27.3, 26.5,
25.6, 25.3, 22.5, 13.9, 13.5, 13.4, 12.4.
Syn th esis of th e P olym er s. A general procedure is as
follows: 400 µmol of 8, 400 µmol of binaphthalene monomer
(m on -(*,*)), 9.2 mg (12.5 µmol) of Pd2dba3, and 30.6 mg (100
µmol) of AsPh3 were dissolved in 30 mL of dry THF. The
mixture was purged with argon and refluxed for 60 h. After
cooling, the polymer was precipitated in methanol, collected
by filtration, and dried. Finally, the polymer was redissolved
in THF, precipitated in methanol, and dried under vacuum.
This procedure was repeated twice.
(10) Mitsunobu, O. Synthesis 1981, 1.
(11) van Pham, C.; Macomber, R. S.; Mark, H. B.; Zimmer, H. J .
Org. Chem. 1984, 49, 5250.
a . Syn th esis of N,N′-Dieth yl-1-[5-[2-[4-[N-eth yl-N-[6-
(ter t-bu tyld im eth yl)silyloxyh exyl]a m in o]p h en yl]eth en -
yl]2-t h ien ylm et h ylid een ]-2,4,6-(1H ,3H ,5H )-p yr im id in e-
tr ion (10b). In a 20 mL flask, equipped with a CaCl2 tube,
156 mg (298 µmol) of 3b and 54.0 mg (358 µmol) of tert-
butyldimethylsilyl chloride were dissolved in 5 mL of dry DMF.
The solution was cooled in an ice bath, and 48.7 g (715 mmol)
of imidazole was added in several portions. The reaction
mixture was stirred overnight at 40 °C. After cooling, water
was added, and the mixture was extracted with diethyl ether.
The combined organic layers were washed with a saturated
(12) Farina, V.; Krishnan, B. J . Am. Chem. Soc. 1991, 113, 9585.
(13) Bao, Z.; Chan, W. K.; Pu, L. J . Am. Chem. Soc. 1995, 117,
12426.
(14) (a) Ma, L.; Hu, Q.-S.; Musick, K. Y.; Vitharana, D.; Wu, C.;
Kwan, C. M. S.; Pu, L. Macromolecules 1996, 29, 5083. (b)
Tour, J . M. Chem. Rev. 1996, 96, 537.
(15) S’heeren, G.; Persoons, A.; Rondou, P.; Wiersma, J .; Van
Beylen, M.; Samyn, C. Makromol. Chem. 1993, 194, 1733.
(16) Hu, Q.-S.; Huang, W.-S.; Vitharana, D.; Zheng, X.-F.; Pu, L.
J . Am. Chem. Soc. 1997, 119, 12454.
MA0351118