5
458 Schimmel et al.
.98 (2 m, 2 × 1 H, CH
Macromolecules, Vol. 35, No. 14, 2002
2
4
7
2
), 4.66-4.71 (m, 1 H, NCH), 4.79-
), 5.57-5.71 (m, 1 H, CHdCH ), 7.14-
Desbene, P. L.; Basselier, J . J .; Richard, D. J . Electroanal.
Chem. 1983, 147, 107-121.
(4) (a) Rooney, J . M. In Comprehensive Polymer Science; Allen,
G., Bevington, J . C., Eastmond, G. C., Ledwith, A., Russo,
S., Sigwalt, P., Eds.; Pergamon Press: Oxford, 1989; Vol. 3,
pp 697-704. (b) For reviews on carbocationic polymerizations,
see references cited in: Baird, M. C. Chem. Rev. 2000, 100,
.96 (m, 2 H, CHdCH
2
2
1
3
.43 (m, 6 H, ArH), 8.04-8.06 (m, 2 H, ArH). C NMR (75.5
): δ 18.7 (q, CH ), 39.1 (t, CH ), 51.1 (d, NCH),
10.0 (br d, Ar), 117.3 (t, CHdCH ), 118.6, 120.2 (2 d, Ar),
23.2 (s, Ar), 125.3 (d, Ar), 134.8 (d, CHdCH ), 139.6 (s, Ar).
MHz, CDCl
1
1
3
3
2
2
2
+
MS (70 eV): m/z (%) 235 (14) [M ], 195 (12), 194 (100), 167
18).
N-Eth ylca r ba zole (10). As described above for the forma-
1
471-1478.
(
(
5) For cationic grafting polymerizations of N-vinylcarbazole (1)
as method for surface modification of inorganic solid materi-
als, see: (a) Spange, S.; Gr a¨ ser, A.; M u¨ ller, H.; Zimmermann,
Y.; Rehak, P.; J a¨ ger, C.; Fuess, H.; Baehtz, C. Chem. Mater.
1
5
tion of 9, a mixture of 7b (253 mg, 1.00 mmol), triethylsilane
232 mg, 2.00 mmol), and trimethylsilyl triflate (222 mg, 1.00
mmol) in dichloromethane reacted to yield 10 (160 mg, 0.82
(
2
001, 13, 3698-3708. (b) Spange, S.; Gr a¨ ser, A.; Huwe, A.;
Kremer, F.; Tintemann, C.; Behrens, P. Chem. Eur. J . 2001,
1
mmol, 82%). H NMR (300 MHz, CDCl
Hz, 3 H, CH ), 4.14 (q, J ) 6.0 Hz, 2 H, CH
H, Ar), 8.02-8.05 (m, 2 H, ArH).22
Kin etics. The employed methods for the kinetic measure-
ments are described in ref 10. Colored solutions of the
3
): δ 1.25 (t, J ) 6.0
7
2
, 3722-3728. (c) Review: Spange, S. Prog. Polym. Sci. 2000,
5, 781-849.
6) Mayr, H.; Patz, M. Angew. Chem. 1994, 106, 990-1010;
Angew. Chem., Int. Ed. Engl. 1994, 33, 938-957.
7) Mayr, H.; Kuhn, O.; Gotta, M. F.; Patz, M. J . Phys. Org.
Chem. 1998, 11, 642-654.
8) Mayr, H.; Patz, M.; Gotta, M. F.; Ofial, A. R. Pure Appl. Chem.
1998, 70, 1993-2000.
(9) Mayr, H.; Bug, T.; Gotta, M. F.; Hering, N.; Irrgang, B.;
J anker, B.; Kempf, B.; Loos, R.; Ofial, A. R.; Remennikov,
G.; Schimmel, H. J . Am. Chem. Soc. 2001, 123, 9500-9512.
10) Mayr, H.; Schneider, R.; Schade, C.; Bartl, J .; Bederke, R. J .
Am. Chem. Soc. 1990, 112, 4446-4454.
11) (a) Mayr, H. In Ionic Polymerizations and Related Processes;
Puskas, J . E., Michel, A., Barghi, S., Paulo, C., Eds.; NATO
Sci. Ser. E Applied Sciences; Kluwer Academic Publishers:
Dordrecht, 1999; Vol. 359, pp 99-115. (b) Mayr, H. In
Cationic Polymerization: Mechanisms, Synthesis and Ap-
plications; Matyjaszewski, K., Ed.; Marcel Dekker: New
York, 1996; pp 51-136.
12) Burfeindt, J .; Patz, M.; M u¨ ller, M.; Mayr, H. J . Am. Chem.
Soc. 1998, 120, 3629-3634.
13) (a) Iminium Salts in Organic Chemistry (Adv. Org. Chem.
Vol. 9); B o¨ hme, H., Viehe, H. G., Eds.; Interscience: New
York, 1976. (b) Mayr, H.; Ofial, A. R.; W u¨ rthwein, E.-U.; Aust,
N. C. J . Am. Chem. Soc. 1997, 119, 12727-12733 and
references therein.
3
2
), 7.14-7.38 (m,
6
(
(
(
9
,12
benzhydrylium tetrafluoroborates 2a ,b
in dichloromethane
with concentrations of (3-7) × 10 mol L-1 were prepared.
An excess (10-300 equiv) of 1 was added, and the reactions
were followed by measuring the decay of absorption. Results
are summarized in Table 4.
-5
-
-
Solutions of the iminium salts 6-SnCl
5
or 6-BCl
4
were
in
(
(
prepared by adding 7b to cooled solutions of BCl
3
or SnCl
4
dichloromethane. An excess of the nucleophilic reaction part-
ner was added, and the reactions were followed by measuring
the decay of conductivity. Results are summarized in Table 5.
Ack n ow led gm en t. We thank the Deutsche Fors-
chungsgemeinschaft and the Fonds der Chemischen
Industrie for financial support.
(
Refer en ces a n d Notes
(
(
1) Pearson, J . In Encyclopedia of Polymer Science and Engineer-
ing; Mark, H. F., Bikales, N. M., Overberger, C. C., Menges,
G., Eds.; Wiley: New York, 1989; Vol. 17, pp 257-294.
2) Reviews: (a) Wang, Q.; Wang, L.; Yu, L. Macromol. Rapid
Commun. 2000, 21, 723-745. (b) Kippelen, B.; Golemme, A.;
Hendrickx, E.; Wang, J . F.; Marder, S. R.; Peyghambarian,
N. In Field Responsive Polymers; ACS Symposium Series;
American Chemical Society: Washington, DC, 1999; Vol. 726,
pp 204-225. (c) Kippelen, B.; Meerholz, K.; Peyghambarian,
N. In Nonlinear Optics of Organic Molecules and Polymers;
Nalwa, H. S., Miyata, S., Eds.; CRC Press: Boca Raton, FL,
(
(
14) A gas-solid reaction of N-vinylcarbazole (1) with HCl gas
and subsequent addition of methanol was performed at -78
°
C to obtain 7a (83%). For analogous reactions, see: (a)
Kaupp, G.; Matthies, D. Chem. Ber. 1987, 120, 1897-1903.
b) Kaup, G.; Matthies, D. Mol. Cryst. Liq. Cryst. 1988, 161,
19-143.
15) Kricka, L. J .; Ledwith, A. J . Org. Chem. 1973, 38, 2240-
241.
(
1
(
(
2
1
997; pp 465-513. (d) Kippelen, B.; Sandalphon; Volodin, B.
16) For analogous reactions, see: Katritzky, A. R.; Zhang, G.;
L.; Meerholz, K.; Peyghambarian, N. In Photonic and Opto-
electronic Polymers; ACS Symposium Series; American Chemi-
cal Society: Washington, DC, 1997; Vol. 672, pp 218-235.
3) For some recent reports, see: (a) Brotherston, I. D.; Mu-
digonda, D. S. K.; Osborn, J . M.; Belk, J .; Chen, J .; Loveday,
D. C.; Boehme, J . L.; Ferraris, J . P.; Meeker, D. L. Electro-
chim. Acta 1999, 44, 2993-3004. (b) Meeker, D. L.; Mu-
digonda, D. S. K.; Osborn, J . M.; Loveday, D. C.; Ferraris, J .
P. Macromolecules 1998, 31, 2943-2946. (c) Geissler, U.;
Hallensleben, M.; Toppare, L. Synth. Met. 1993, 55, 1662-
Qi, M.; Xie, L. Tetrahedron Lett. 1997, 38, 6959-6960.
(17) Mayr, H.; Ofial, A. R. Tetrahedron Lett. 1997, 38, 3503-3506.
(18) B o¨ ttger, G. M.; Fr o¨ hlich, R.; W u¨ rthwein, E.-U. Eur. J . Org.
Chem. 2000, 1589-1593.
(
(19) Rooney, J . M. Makromol. Chem. 1978, 179, 165-171.
(20) Bowyer, P. M.; Ledwith, A.; Sherrington, D. C. Polymer 1971,
12, 509-520.
(
21) Rodriguez, M.; Le o´ n, L. M. Eur. Polym. J . 1983, 19, 585-
5
88.
1
667. (d) Desbene-Monvernay, A.; Lacaze, P. C.; Dubois, J .
E.; Desbene, P. L. J . Electroanal. Chem. 1983, 152, 87-96.
e) Lacaze, P. C.; Dubois, J . E.; Desbene-Monvernay, A.;
(22) Flo, C.; Pindur, U. Liebigs Ann. Chem. 1987, 509-513.
(
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