U. Herzog, R. West
FULL PAPER __________________________________________________________________________
C: 68.8 ppm, D: 20.4 ppm (1JSiC: 68 Hz),
E: 22.7 ppm, F : 32.4 ppm, G: 31.7 ppm,
H: 28.8 ppm, I: 22.4 ppm, J: 14.1 ppm,
i: 158.8 ppm, o: 129.5 ppm, m: 114.5 ppm,
p: 120.8 ppm
SiCl2 were added to this dispersion within 5 min. The sodium
turned pink and later deep blue. After 1 h of intensive stirring
at 110 °C the mixture was allowed to cool to room tempera-
ture before 3 ml isopropanol and finally 250 ml methanol
were added carefully. The light blue residue of polymer and
NaCl were dissolved in 40 ml toluene. The solution was fil-
tered from the light blue NaCl, and the polymer was precipi-
tated by adding of 100 ml MeOH to yield 5 g crude product.
The polymer was redissolved in 40 ml toluene and precipitat-
ed with 40 ml MeOH to yield 3.5 g (22%) of a white, almost
solid polysilane after drying in vacuo.
Phenoxypropyl-phenyldichlorosilane (2e)
Under nitrogen 16.0 g (0.12 mol) allyl phenyl ether were
mixed with 17.7 g (0.10 mol) PhSiHCl2, and 2 drops of a
solution of 20 mg H2PtCl6 · 6H2O in isopropanol were added.
After stirring over night the reaction mixture turned black,
and the fractionated distillation in vacuo gave at first 4 g allyl
phenyl ether and than 26.7 g (86%) 2e at 165–190 °C/ 0.5
torr). 1 ml black oily residue remained.
All other polysilanes were prepared using the same proce-
dure. The yields of polysilanes after fractionation were 3a:
7.5%, 3b: 7%, 3c: 5%, 3d: 12%, 3e: 29%.
PhbO–CCH2–CBH2–CAH2–SiCl2–Pha
1H NMR: A: 1.48 ppm (3JHH: 8.3 Hz), B: 1.98 ppm,
C: 3.89 ppm (3JHH: 6.3 Hz, 1JCH: 142 Hz),
Pha: o: 7.70 ppm (3JHH: 7.6 Hz), m: 7.39 ppm,
p: 7.43 ppm (3JHH: 7.2 Hz), Phb: o: 6.83 ppm
References
[1] a) R. West in Comprehensive Organometallic Chemistry; E.
Abel (Ed.), Pergamon Press Ltd., Oxford, England (1982),
Ch. 9.4, p. 365; b) R. West in The Chemistry of Organosili-
con Compounds, S. Patai, Z. Rappoport (Eds.), Wiley (1989),
Ch. 19, p. 1207; c) R. D. Miller, J. Michl, Chem. Rev. 1989,
89, 1359
[2] a) J. P. Wesson, T.C. Williams, J. Polym. Sci., Polym. Chem.
Ed. 1980, 18, 959; b) R. E. Trujillo, J. Organomet. Chem.
1980, 198, C27; c) R. West, L. D. David, P. I. Djurovich, D.
L. Stearly, K. S. V. Srinivasan, H. Yu, J. Am. Chem. Soc.
1981, 103, 1352; d) R. D. Miller, D. Thompson, R. Sooriya-
kumaran, G. N. Fickes, J. Polym. Sci. A 1991, 29, 813; e) R.
G. Jones, R. E. Benfield, R. H. Cragg, A. C. Swain, S. J.
Webb, Macromolecules 1993, 26, 4878
[3] a) H. Frey, G. J. J. Out, M. Möller, D. Greszta, K. Matyjas-
zewski, Macromolecules 1993, 26, 6231; b) C.-H. Yuan, R.
West, Macromolecules 1993, 26, 2645; c) S. S. Bukalov, M.
V. Teplitsky, L. A. Leites, C.-H. Yuan, R. West, Mendeleev
Comm. 1996, 135; d) K. Oka, N. Fujiue, S. Nakanishi, T.
Takata, T. Dohmaru, C.-H. Yuan, R. West, Chem. Lett. 1995,
875
[4] a) M. M. Despotopoulou, C. W. Frank, R. D. Miller, J. F.
Rabolt, Macromolecules 1996, 29, 5797; b) K. Obata, M.
Kira, Macromolecules 1998, 31, 4666
[5] C.-H. Yuan, R. West, Macromolecules 1994, 27, 629
[6] C.-H. Yuan, R. West, Macromolecules 1998, 31, 1087
[7] R. G. Jones, R. E. Benfield, P. J. Evans, S. J. Holder, J. A. M.
Locke, J. Organomet. Chem. 1996, 521, 171
[8] a) R. West, J. Organomet. Chem. 1986, 300, 327; b) S. Irie,
M. Irie, Macromolecules 1997, 30, 7906
[9] U. Herzog, R. West, Macromolecules 1999, 32, 2210
[10] A. J. Lovinger, D. D. Davis, F. C. Schilling, F. A. Bovey, J.
M. Zeigler, Polym. Commun. 1989, 30, 356
[11] F. C. Schilling, F. A. Bovey, A. J. Lovinger, J. M. Zeigler,
Macromolecules 1986, 19, 2660
(3JHH: 7.9 Hz), m: 7.23 ppm, p: 6.90 ppm(3JHH
:
7.2 Hz)
13C NMR: A: 17.1 ppm (1JSiC: 71.2 Hz), B: 22.6 ppm,
C: 68.6 ppm, Pha: i: 132.2 ppm, o: 133.3 ppm,
m: 128.4 ppm, p: 131.7 ppm Phb: i: 158.7 ppm,
o: 129.4 ppm, m: 114.4 ppm, p: 120.7 ppm
29Si NMR: 19.15 ppm
Bis(phenoxypropyl)dichlorosilane (2f)
Under nitrogen 24.5 g (0.183 mol) allyl phenyl ether were
mixed with a solution of 9.3 g H2SiCl2 (0.092 mol) in xylene
(25 mass-% H2SiCl2), and 2 drops of a solution of 20 mg
H2PtCl6 · 6H2O in isopropanol were added. After stirring for
two days the product was distilled in vacuo to give at first
xylene and some allyl phenyl ether, next approximately 5 ml
at 120–125 °C/0.5 torr (mainly PhO(CH2)3SiHCl2) and fi-
nally 20.5 g (61%) 2f (Kp. 180–210 °C / 0.5 torr). 1 ml black
oily residue remained.
[PhO–CCH2–CBH2–CAH2-]2SiCl2
1H NMR: A: 1.26 ppm (3JHH: 8.3 Hz), B: 1.96 ppm,
C: 3.88 ppm (3JHH: 6.1 Hz)
ArH: o: 6.85 ppm (3JHH: 8.6 Hz), m: 7.24 ppm,
p: 6.91 ppm (3JHH: 7.5 Hz)
13C NMR: A: 16.7 ppm (1JCH: 122 Hz, 2JCH: 4.0 Hz,
1JSiC: 76.3 Hz), B: 22.5 ppm (1JCH: 129 Hz,
2JSiC: 8.0 Hz), C: 68.6 ppm (1JCH: 143 Hz,
2JCH: 4.0 Hz), i: 158.7 ppm, o: 129.4 ppm
(1JCH: 158.5 Hz, 2JCH: 8.7 Hz, 3JCH: 1.5 Hz),
m: 114.4 ppm (1JCH: 158.5 Hz), p: 120.7 ppm
(1JCH: 160 Hz)
29Si NMR: 33.4 ppm
PhO–CH2–CH2–CH2–SiHCl2: H NMR: SiH: 5.55 ppm
(3JHH: 2.0 Hz); 29Si NMR: 10.7 ppm
1
Address for correspondence:
Dr. U. Herzog
Technische Universität Bergakademie Freiberg
Institut für Anorganische Chemie
Leipziger Straße 29
D-09596 Freiberg
Fax: Internat. code (0)3731-394058
e-Mail: herzog@merkur.hrz.tu-freiberg.de
Wurtz Condensation
Preparation of {[PhO(CH2)3]2Si}n (3f) as a typical example
2.76 g (0.12 mol) Na and 50 ml toluene were heated until
110°C and stirred under Ar. 20 g (0.054 mol) [PhO(CH2)3]2
32
J. Prakt. Chem. 2000, 342, No. 1