H. Seki et al. / Journal of Organometallic Chemistry 696 (2011) 846e851
851
1H NMR (CDCl3)
29Si NMR (CDCl3)
d
0.41 (s, 12H). 13C NMR (CDCl3)
d
ꢁ2.20, 122.8.
4.8. Synthesis of syn-1,3,9,11-tetramethyl-5,5,7,7,13,13,15,
d
ꢁ60.0. MS (70 eV) m/z 389 (MþeMe,15). IR (CCl4
15-octaphenyltricyclo[9.5.1.13,9]octasiloxane (5)
solution) 2975, 2290, 1270, 1110 cmꢁ1
.
A two-necked flask equipped with a reflux condenser was
charged with 1 (0.40 g, 1.0 mmol) and THF 5 mL, while pyridine
(0.32 g, 4.0 mmol) was added to the flask and subjected to stirring
at room temperature for 30 min. A solution of 3 (0.82 g, 2.0 mmol)
in THF 5 mL was added to the mixture and subjected to stirring at
room temperature for 6 h. Cyanuric acid was filtered out, and the
organic layer was then washed with diluted hydrochloric acid two
times. The organic layer was then washed with water two times
and dried over anhydrous magnesium sulfate. After filtration, the
solvent was removed in vacuo and washed with methanol two
times. The product was dried under reduced pressure to give 5 as
a white solid (52% yield, 0.55 g). Recrystallization by the solvent
evaporation method using diethyl ether/acetone ¼ 2/1 gave a single
crystal as a colorless plate.
4.4. Preparation of 1,1,3,3-tetraphenyldisiloxane-1,3-diol (3)
A solution of water (3.60 g, 0.20 mol) in THF (70 mL) was slowly
added to a vigorously stirred and ice-cooled (0 ꢀC) solution of
dichloro(diphenyl)silane (100.8 g, 0.40 mol) in THF (70 mL), and the
mixture was then refluxed for 3 h. The solvent was removed, and the
residue was distilled in vacuo to give 1,3-dichloro-1,1,3,3-tetraphe-
nyldisiloxane as a colorless liquid in 41% yield (b.p. 215e224 ꢀC/
0.12 Torr).
A solution of 1,3-dichloro-1,1,3,3-tetraphenyldisiloxane (9.02 g,
20 mmol) in diethyl ether (80 mL) was added to a vigorously stirred
and ice-cooled (0 ꢀC) mixture of water (0.72 g, 40 mmol), trie-
thylamine (4.04 g, 40 mmol), diethyl ether (100 mL), and acetone
(25 mL), followed by stirring at room temperature for 30 min.
Triethylamine hydrogen chloride was filtered out, and solvent was
evaporated. The solution was poured into hexane with vigorous
stirring, and the precipitate was filtered. The precipitate was sub-
jected to recrystallization from benzene/petroleum ether to give 3
as a white plate (81% yield, 6.72 g).
M.p. 170.2e170.7 ꢀC 1H NMR (acetone-d6/ppm)
6.95e7.67 (m, 40H). 13C NMR (acetone-d6/ppm)
ꢁ3.3, 128.5, 128.7,
d 0.14 (s, 12H),
d
130.8, 131.1, 134.8, 134.9, 135.7. 29Si NMR (acetone-d6/ppm)
d
ꢁ44.4,
ꢁ62.8. IR (CCl4 solution/cmꢁ1) 3073, 3052, 2971, 1593, 1430, 1270,
1128, 1055, 1027, 865, 521. MS (FABþ) m/z 1061 [M þ H]þ Anal.
Calcd. for C52H52O10Si8; C, 58.83; H, 4.94. Found; C, 58.87; H, 5.00.
M.p. 111.9e112.6 ꢀC 1H NMR (acetone-d6/ppm)
7.23 (t, 7.0 Hz, 8H), 7.34 (t, 7.0 Hz, 4H), 7.55 (d, 7.0 Hz, 8H). 13C NMR
(acetone-d6/ppm)
128.4, 130.5, 135.2, 137.3. 29Si NMR (acetone-d6/
ppm)
ꢁ39.5. IR (KBr disk) 3425, 3071, 1429, 1126, 1089, 886, 847,
697, 512 cmꢁ1
d 4.06 (s, 2H),
Appendix A. Supplementary material
d
d
CCDC 794551, and 794552 contain the supplementary crystal-
lographic data for 4, and 5. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre via www.
with this article can be found, in the online version, at doi:10.1016/j.
.
4.5. Synthesis of 1/1 adduct of 1 with nucleophile
Typically, four equivalents of nucleophile (HMPT, DMF, pyridine,
and triphenylphosphine) were added to a diethyl ether solution of
1, and the mixture was cooled to 0 ꢀC. No precipitates were formed
till 1 day.
References
[1] J.F. Brown Jr., L.H. Vogt Jr., A. Katchman, J.W. Eutance, K.W. Krantz, J. Am.
Chem. Soc. 82 (1960) 6194.
[2] R.H. Baney, M. Itoh, A. Sakakibara, T. Suzuki, Chem. Rev. 95 (1995) 1409.
[3] C.L. Frye, J.M. Klosowski, J. Am. Chem. Soc. 93 (1971) 4599.
[4] (a) E.-C. Lee, Y. Kimura, Polym. J. 29 (1997) 678;
4.6. NMR studies of 1 with nucleophiles
Typically, an equivalent nucleophile (HMPT, DMF, pyridine, and
acetonitrile) and 1 were added together in CDCl3. Measurements
were recorded at appropriate intervals at room temperature.
(b) E.-C. Lee, Y. Kimura, Polym. J. 30 (1998) 234;
(c) W.-Y. Chen, Y. Lin, K.P. Pramoda, K.X. Ma, T.S. Shung, J. Polym. Sci. B. Polym.
Phys. 38 (2000) 138;
(d) S. Hayashida, S. Imamura, J. Polym. Sci. A: Polym. Chem. 33 (1995) 55.
[5] M. Itoh, Silicon Chem. Jpn. 15 (2001) 19.
[6] (a) N.N. Sokolov, K.A. Andrianov, S.M. Akimova, Zh. Obshch. Khim 26 (1956) 933;
(b) J.F. Harrod, E. Pelletier, Organometallics 3 (1984) 1064;
4.7. Synthesis of 2,4,6,8-tetramethyl-2,4,6,8-tetrakis-
(triphenylsiloxy)cyclotetrasiloxane (4)
(c) E. Pelletier, J.F. Harrod, Organometallics 3 (1984) 1070.
[7] M. Unno, S. Chang, H. Matsumoto, Bull. Chem. Soc. Jpn. 78 (2005) 1105.
[8] Y. Abe, K. Suyama, T. Gunji, Chem. Lett. 35 (2006) 114.
[9] K. Suyama, T. Gunji, K. Arimitsu, Y. Abe, Organometallics 25 (2006) 5587.
[10] H. Seki, T. Kajiwara, Y. Abe, T. Gunji, J. Organomet. Chem. 695 (2010) 1363.
[11] R. Ito, Y. Yamazaki, Y. Kawakami, Chem. Lett. 38 (2009) 364.
[12] (a) J.F. Brown Jr., L.H. Vogt Jr., J. Am. Chem. Soc. 87 (1965) 4313;
(b) V.E. Shklover, Y.u.T. Struchkov, Usp. Khim 49 (1980) 518;
(c) V.E. Shklover, I.Y.u. Klement’ev, Y.u.T. Struchkov, Dokl. Akad. Nauk. SSSR
259 (1981) 131.
[13] (a) M. Unno, K. Takada, H. Matsumoto, Chem. Lett. 27 (1998) 489;
(b) M. Unno, A. Suto, K.Takada, H. Matsumoto, Bull. Chem. Soc. Jpn. 73(2000)215.
[14] R. Corriu, M. Henner Leard, J. Organomet. Chem. 64 (1974) 351.
[15] R.J.P. Corriu, F. Larcher, G. Royo, J. Organomet. Chem. 104 (1976) 293.
[16] R.J.P. Corriu, C. Guerin, Adv. Organomet. Chem. 2 (1982) 265.
[17] R.J.P. Corriu, C. Guerin, J.J.E. Moreau, Top. Stereochem. 15 (1984) 43.
[18] J. Chojnowski, M. Cypryk, M. Michalski, J. Organomet. Chem. 161 (1978) C31.
[19] A.R. Bassindale, J.C.-Y. Lau, P.G. Taylor, J. Organomet. Chem. 341 (1988) 213.
[20] H. Sakurai, Organometallics. in: H. Nozaki, S. Yamamoto, J. Tsuji, R. Noyori
(Eds.), Kagaku Zokan, vol. 105. Kagaku Dojin, Kyoto, 1985, p. 33.
[21] (a) J.H. Campbell-Ferguson, A.E. Ebsworth, J. Chem. Soc. A (1967) 705;
(b) Y.J. Corey, J.R. West, J. Am. Chem. Soc. 85 (1963) 4034.
A two-necked flask equipped with a reflux condenser was
charged with 1 (0.20 g, 0.50 mmol) and THF 2 mL, while pyridine
(80 mL, 1.0 mmol) was added to the flask and subjected to stirring at
room temperature for 30 min. Triphenylsilanol (0.69 g, 2.5 mmol)
was added to the mixture and refluxed for 12 h. Diethyl ether was
added and washed with diluted hydrochloric acid two times. The
organic layer was washed with water two times and dried over
anhydrous magnesium sulfate. After filtration, the solvent was
removed in vacuo, affording the product as an oil. The compound
was purified by column chromatography (silica gel, hexane/
CHCl3 ¼ 7/3), affording 4 as a white solid (0.38 g, 57% yield).
Recrystallization by the solvent evaporation method using CHCl3/
acetone ¼ 1/1 gave a single crystal as a colorless plate.
M.p. 194.5e195.1 ꢀC 1H NMR (CDCl3/ppm)
d
ꢁ0.15 (s, 12H), 7.03
(t, J ¼ 7.6 Hz, 24H), 7.21 (tt, J ¼ 7.8, 1.5 Hz, 12H), 7.50 (dd, J ¼ 7.6,
1.5 Hz, 24H). 13C NMR (CDCl3/ppm)
d
ꢁ2.5, 127.6, 129.6, 135.0, 135.3.
29Si NMR (CDCl3/ppm)
d
ꢁ20.5, ꢁ65.7. MS-ESIþ m/z ¼ 1360.3
[22] F.J. Feher, J.J. Schwab, D. Soulivong, J.W. Ziller, Main Group Chem. 2 (1997) 123.
[23] M. Ronchi, M. Pizzotti, A.O. Biroli, P. Macchi, E. Lucenti, C. Zucchi, J. Organo-
met. Chem. 692 (2007) 1788.
[24] N.L. Allinger, Using MM2 with ChemDraw pro version 11.0, J. Comput. Chem.
14 (1993) 755.
[M þ Na]þ. IR (CCl4/cmꢁ1) 3071, 3052, 1429, 1271, 1119, 1052, 713,
700, 515. Anal. Calcd. for C76H72O8Si8; C, 68.22; H, 5.42. Found; C,
68.07; H, 5.38.