1284
J. M. Pollino, M. Weck
PAPER
mL), 2 N NaOH (100 mL), and brine (100 mL). Drying (Na2SO4)
followed by recrystallization from EtOH provided pure 17 (647 mg,
86%) as a white crystalline solid.
1H NMR (CDCl3): = 8.84 (d, 2 H, J = 5.5 Hz, Pyr H), 8.02 (d, 2
H, J = 5.5 Hz, Pyr H), 7.61 (d, 2 H, J = 8.2 Hz, ArH), 7.51(d, 2 H,
J = 8.2 Hz, ArH), 7.27 (d, 2 H, J = 8.2 Hz, ArH), 6.98 (d, 2 H,
J = 8.2 Hz, ArH), 4.01 (t, 2 H, J = 6.6 Hz, CH2O), 1.85–1.75 (m, 2
H, CH2), 1.58–1.46 (m, 2 H, CH2), 1.00 (t, 3 H, J = 7.6 Hz, CH3)
(m, 6 H, SC6H5), 6.90 (d, 4 H, J = 8.8 Hz, ArH), 6.67 (s, 2 H, ArH),
5.50–5.13 (br m, 2 H, CH=C), 4.68 (br s, 4 H, CH2S), 3.96–3.86 (m,
4 H, OCH2), 3.33 (m, 2 H, CH2NH), 3.24–2.30 (br m, 3 H), 2.03–
1.10 (m, 34 H), 0.96 (t, 3 H, J = 7.1 Hz, CH3).
13C NMR (CD2Cl2): = 174.8, 160.4, 158.8, 158.4, 151.7, 151.2,
137.7, 133.5, 131.8, 131.6, 130.9, 130.7, 127.9, 124.4, 120.1, 115.2,
110.1, 110.0, 68.8, 68.5, 68.3, 64.9, 51.7, 48.6, 46.1, 43.0, 36.5,
36.1, 31.9, 30.2, 30.0, 29.8, 29.7, 29.5, 29.2, 27.1, 26.6, 26.2, 19.8,
14.2.
13C NMR (CDCl3): = 163.8, 158.9, 150.8, 149.3, 139.2, 136.7,
132.4, 128.1, 127.8, 123.2, 121.5, 114.8, 67.7, 31.3, 19.2, 13.8.
MS (EI): m/z (%) = 347.156 (M+, calcd. 347.152).
Acknowledgements
Anal. Calcd for C22H21NO3: C, 76.06; H, 6.09; N, 4.03. Found: C,
75.92; H, 6.07; N, 3.93.
Acknowledment is made to the donors of The Petroleum Research
Fund, administered by the ACS for partial support of this research.
M. W. gratefully acknowledges a 3M Untenured Faculty Award. J.
M. P. would like to thank Dr. R. Kriegel and Dr. L. P. Stubbs for
their stimulating discussions pertaining to this work.
Polymers 18–21; General Procedure
The desired mesogen 14, 16, 17 (0.100 mmol) or commercially
available 4 -(pentyloxy)-4-biphenylcarbonitrile (18; 0.100 mmol)
was added to a solution of polymer 11 (0.100 mmol) in CH2Cl2 (10
mL) and stirred at r.t. One equivalent of AgBF4(aq) (19.49 L of a
5.13 M stock solution, 0.100 mmol) was added to the 1:1 mixture at
which point AgCl precipitated from the solution. The mixture was
stirred for an additional 10 min, filtered over Celite, and the solvent
was removed in vacuo to provide the self-assembled polymers 18–
21 in quantitative yield.
References
(1) Odian, G. Principles of Polymerization, 3rd ed.; Wiley: New
York, 1991.
(2) Lindsey, J. S. New J. Chem 1991, 15, 153.
(3) Philip, D.; Stoddart, J. F. Angew. Chem., Int. Ed. Engl. 1996,
35, 1154.
(4) Stang, P.; Olenyuk, B. Acc. Chem. Res. 1997, 30, 502.
(5) Brunsveld, L.; Folmer, B. J. B.; Meijer, E. W.; Sijbesma, R.
P. Chem. Rev. 2001, 101, 4071.
(6) Aakeröy, C. B.; Beatty, A. M.; Lorimer, K. R. J. Chem. Soc.,
Dalton Trans. 2000, 3869.
(7) Archer, R. D. Coord. Chem. Rev. 1993, 128, 49.
(8) Holliday, B. J.; Mirkin, C. A. Angew. Chem. Int. Ed. 2001,
40, 2022.
(9) Swiegers, G. F.; Malefetse, T. J. Chem. Rev. 2000, 100,
3483.
(10) Zaworotko, M. J. Angew. Chem. Int. Ed. 1998, 37, 1211.
(11) Albrecht, M.; Gossage, R. A.; Lutz, M.; Spek, A. L.; van
Koten, G. Chem.–Eur. J. 2000, 6, 1431.
(12) Albrecht, M.; Lutz, M.; Antoine, M. M. S.; Lutz, E. T. H.;
Spek, A. L.; van Koten, G. J. Chem. Soc., Dalton Trans.
2000, 3797.
(13) Albrecht, M.; van Koten, G. Angew. Chem. Int. Ed. 2001, 40,
3750.
(14) Huck, W. T. S.; Hulst, R.; Timmerman, P.; van Veggel, F. C.
J. M.; Reinhoudt, D. N. Angew. Chem., Int. Ed. Engl. 1997,
36, 1006.
Polymer 18
1H NMR (CD2Cl2): = 7.89 (m, 4 H, SC6H5), 7.64 (d, 4 H, J = 8.2
Hz, ArH), 7.54 (d, 2 H, J = 8.8 Hz, ArH), 7.53 (m, 6 H, SC6H5), 6.98
(d, 2 H, J = 8.8 Hz, ArH), 6.69 (s, 2 H, ArH), 5.50–5.20 (br m, 2 H,
CH=C), 4.71 (br s, 4 H, CH2S), 3.99 (t, 2 H, J = 6.6 Hz, OCH2),
3.98–3.85 (m, 4 H, OCH2), 3.24–2.30 (br m, 3 H), 2.03–1.00 (m, 28
H), 0.93 (t, 3 H, J = 6.6, 7.1 Hz, CH3).
13C NMR (CD2Cl2): = 175.1, 160.8, 158.6, 150.9, 133.6, 132.6,
132.8, 131.8, 131.3, 130.9, 128.9, 127.6, 115.6, 110.4, 110.3, 68.9,
68.7, 64.7, 51.8, 48.6, 46.1, 43.0, 36.5, 36.1, 30.2, 30.0, 29.8, 29.4,
29.3, 28.6, 26.6, 23.0, 14.4.
Polymer 19
1H NMR (CD2Cl2): = 7.79 (m, 4 H, SC6H5), 7.48–7.43 (m, 10 H,
SC6H5 + ArH), 6.92 (d, 4 H, J = 7.1 Hz, ArH), 6.60 (s, 2 H, ArH),
5.50–5.15 (br m, 2 H, CH=C), 4.57 (br s, 4 H, CH2S), 3.97 (t, 2 H,
J = 6.6 Hz, OCH2), 3.96–3.83 (m, 4 H, OCH2), 3.24–2.30 (br m, 3
H), 2.37 (t, 2 H, J = 7.1 Hz, CH2CN), 2.03–1.12 (m, 32 H), 0.97 (t,
3 H, J = 7.1 Hz, CH3).
13C NMR (CD2Cl2): = 174.7, 160.3, 158.9, 158.5, 151.1, 133.8,
133.3, 131.7, 131.2, 130.8, 130.6, 127.9, 115.2, 110.3, 110.2, 68.3,
67.7, 65.0, 51.5, 48.6, 46.1, 43.0, 36.5, 36.1, 31.9, 30.1, 29.9, 29.7,
29.2, 28.7, 26.5, 25.6, 24.7, 19.8, 18.0, 14.2.
(15) Huck, W. T. S.; Prins, L. J.; Fokkens, R. H.; Nibbering, N.
M. M.; van Veggel, F. C. J. M.; Reinhoudt, D. N. J. Am.
Chem. Soc. 1998, 120, 6240.
(16) Huck, W. T. S.; Snellink-Ruel, B.; van Veggel, F. C. J. M.;
Reinhoudt, D. N. Organometallics 1997, 16, 4287.
(17) Huck, W. T. S.; van Veggel, F. C. J. M.; Kropman, B. L.;
Blank, D. H. A.; Keim, E. G.; Smithers, M. M. A.;
Reinhoudt, D. N. J. Am. Chem. Soc. 1995, 117, 8293.
(18) Huck, W. T. S.; van Veggel, F. C. J. M.; Reinhoudt, D. N.
Angew. Chem., Int. Ed. Engl. 1996, 35, 1213.
(19) Pollino, J. M.; Weck, M. Org. Lett. 2002, 4, 753.
(20) van Manen, H.-J.; Nakashima, K.; Shinkai, S.; Kooijman,
H.; Spek, A. L.; van Veggel, F. C. J. M.; Reinhoudt, D. N.
Eur. J. Inorg. Chem. 2000, 2533.
(21) Errington, J.; McDonald, W. S.; Shaw, B. L. J. Chem. Soc.,
Dalton Trans. 1980, 2312.
(22) Loeb, S. J.; Shimizu, G. K. H. J. Chem. Soc., Chem.
Commun. 1993, 1395.
(23) Trnka, T. M.; Grubbs, R. H. Acc. Chem. Res. 2001, 34, 18.
(24) Fürstner, A. Angew. Chem. Int. Ed. 2000, 39, 3012.
Polymer 20
1H NMR (CD2Cl2): = 8.35 (s, 2 H, Pyr H), 7.95 (d, 2 H, J = 5.5
Hz, Pyr H), 7.68 (d, 4 H, J = 7.1, SC6H5), 7.60 (d, 2 H, J = 7.7 Hz,
ArH), 7.51 (d, 2 H, J = 8.2 Hz, ArH), 7.44–7.40 (m, 6 H, SC6H5),
7.23 (d, 2 H, J = 7.7 Hz, ArH), 6.96 (d, 2 H, J = 8.2 Hz, ArH), 6.69
(s, 2 H, ArH), 5.50–5.13 (br m, 2 H, CH=C), 4.78 (br s, 4 H, CH2S),
3.99 (t, 2 H, J = 6.6 Hz, OCH2), 3.95–3.88 (m, 4 H, OCH2), 3.24–
2.30 (br m, 3 H), 2.03–1.10 (m, 26 H), 0.98 (t, 3 H, J = 7.1 Hz, CH3).
13C NMR (CD2Cl2): = 175.0, 162.7, 159.6, 158.5, 152.1, 151.6,
149.6, 147.2, 139.9, 132.6, 131.7, 131.0, 130.9, 128.6, 128.2, 126.1,
121.9, 115.4, 110.2, 110.1, 68.8, 68.4, 64.7, 52.0, 48.6, 46.1, 43.0,
36.5, 36.1, 31.8, 30.2, 29.8, 29.3, 26.6, 19.8, 14.2.
Polymer 21
1H NMR (CD2Cl2): = 8.05 (s, 2 H, Pyr H), 7.66 (m, 4 H, SC6H5),
7.56 (d, 2 H, J = 6.6 Hz, Pyr H), 7.43 (d, 4 H, J = 7.1 Hz, ArH), 7.39
Synthesis 2002, No. 9, 1277–1285 ISSN 0039-7881 © Thieme Stuttgart · New York