PAPER
2-Aryl-1,1-bis(trimethylsilyl)ethenes
3847
HRMS (EI): m/z [M]+ calcd for C14H23ClSi2: 282.1027; found:
282.1003.
geometry16 and refined as ‘riding model’. The isotropic displace-
ment parameters of hydrogen atoms were set at 1.2 (1.3 for methyl
groups) times the equivalent displacement parameters of appropri-
ate carrier atoms. In both symmetry-independent molecules the py-
ridine ring was found to be disordered; the disorder is connected
with the rotation by 180° around C3–C6 axis and results in two al-
ternative positions of nitrogen atom. The site occupation factors re-
fined at 0.66(2)/0.34(2) in molecule A and 0.70(2)/0.30(2) in
molecule B. Weak restraints for the anisotropic displacement pa-
rameters of disordered atoms were applied.
2-(4-Chlorophenyl)-1,1-bis(trimethylsilyl)ethene (2h)
Colorless oil; yield: 1.16 g (82%).
1H NMR (CDCl3): d = –0.03 (s, 9 H, SiCH3), 0.19 (s, 9 H, SiCH3),
7.12 (d, J = 8.1 Hz, 2 H, Ph), 7.27 (d, J = 8.4 Hz, 2 H, Ph), 7.66 (s,
1 H, =CH).
13C NMR (CDCl3): d = 0.6 (SiCH3), 2.1 (SiCH3), 127.8, 129.1,
132.7, 141.0 (Ar), 147.6 (CH=), 153.2 (C=).
MS (EI): m/z (%) = 282 ([M]+, 5), 193 (30), 169 (60), 159 (55), 73
(100).
Acknowledgment
HRMS (EI): m/z [M]+ calcd for C14H23ClSi2: 282.1027; found:
282.1035.
Financial support from the Ministry of Science and Higher Educa-
tion (Poland); Grant NN 204 238734 is gratefully acknowledged.
2-(4-Bromophenyl)-1,1-bis(trimethylsilyl)ethene (2i)
Colorless oil; yield: 1.39 g (85%).
References
1H NMR (CDCl3): d = –0.08 (s, 9 H, SiCH3), 0.78 (s, 9 H, SiCH3),
7.03–7.06 (m, 2 H, Ar), 7.42 (dd, 2 H, Ar), 7.60 (s, 1 H, =CH).
(1) Pawluć, P.; Hreczycho, G.; Marciniec, B. J. Org. Chem.
2006, 71, 8676; and references cited therein.
(2) (a) Gröbel, B. T.; Seebach, D. Angew. Chem., Int. Ed. Engl.
1974, 13, 83. (b) Seebach, D.; Bürstinghaus, R.; Gröbel, B.
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(c) Inoue, A.; Kondo, J.; Shinokubo, H.; Oshima, K. Chem.
Commun. 2002, 114.
(3) (a) Inoue, A.; Kondo, J.; Shinokubo, H.; Oshima, K. J. Am.
Chem. Soc. 2001, 123, 11109. (b) Hodgson, D. M.; Comina,
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(4) Cuadrado, P.; Gonzales-Nogal, A. M.; Sarmentero, M. A.
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(5) Hudrlik, P. F.; Agwaramgbo, E. L. O.; Hudrlik, A. M.
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(6) Safa, K. D.; Samani, S. P.; Tofangdarzedeh, S.; Hassanpour,
A. J. Organomet. Chem. 2008, 693, 2004.
13C NMR (CDCl3): d = 0.6 (SiCH3), 2.1 (SiCH3), 120.8, 129.4,
135.4, 141.5 (Ar), 130.7 (CH=), 153.1 (C=).
MS (EI): m/z (%) = 326 ([M]+, 5), 311 (40), 237 (100), 213 (30), 159
(50), 73 (100).
HRMS: m/z [M]+ calcd for C14H23BrSi2: 326.0522; found:
326.0520.
2-(3-Pyridyl)-1,1-bis(trimethylsilyl)ethene (2j)
White crystals; yield: 0.92 g (74%).
1H NMR (CDCl3): d = –0.05 (s, 9 H, SiCH3), 0.20 (s, 9 H, SiCH3),
7.20–7.24 (m, 1 H, Ar), 7.45–7.49 (m, 1 H, Ar), 7.65 (s, 1 H, =CH),
8.44–8.49 (m, 2 H, Ar).
13C NMR (CDCl3): d = 0.5 (SiCH3), 2.1 (SiCH3), 122.5, 148.0,
148.6, 150.2 (Ar), 134.8 (CH=), 138.1 (C=).
MS (EI): m/z (%) = 248 ([M – 1]+, 60), 234 (75), 176 (22), 160 (25),
136 (16), 73(100).
(7) Pawluć, P.; Hreczycho, G.; Walkowiak, J.; Marciniec, B.
Synlett 2007, 2061.
(8) Pawluć, P.; Madalska, M.; Hreczycho, G.; Marciniec, B.
Synthesis 2008, 3687.
HRMS: m/z [M]+ calcd for C13H23NSi2: 249.1291; found: 249.1301.
(9) Prukała, W.; Pawluć, P.; Posała, K.; Marciniec, B. Synlett
2008, 41.
2-(2-Thienyl)-1,1-bis(trimethylsilyl)ethene (2k)
(10) (a) Inoue, A.; Kondo, J.; Shinokubo, H.; Oshima, K. Chem.
Lett. 2001, 956. (b) Ohmiya, H.; Yorimitsu, H.; Oshima, K.
Angew. Chem. Int. Ed. 2005, 44, 3488. (c) Kondo, J.; Inoue,
A.; Shinokubo, H.; Oshima, K. Tetrahedron Lett. 2002, 43,
2399.
(11) (a) Gröbel, B. T.; Seebach, D. Chem. Ber. 1977, 110, 852.
(b) Fleming, I.; Floyd, C. D. J. Chem. Soc., Perkin Trans. 1
1981, 969. (c) Jones, A. C.; Sanders, A. W.; Sikorski, W. H.;
Jansen, K. L.; Reich, H. J. J. Am. Chem. Soc. 2008, 130,
6060. (d) Safa, K. D.; Namvari, M. P.; Hassanpour, A.;
Tofangdarzedeh, S. J. Organomet. Chem. 2009, 694, 2448.
(12) (a) Molander, G. A.; Romero, J. A. C.; Corrette, C. P.
J. Organomet. Chem. 2002, 647, 225. (b) Sanada, T.; Kato,
T.; Mitani, M.; Mori, A. Adv. Synth. Catal. 2006, 348, 51.
(13) Pawluć, P.; Marciniec, B.; Hreczycho, G.; Gaczewska, B.;
Itami, Y. J. Org. Chem. 2005, 70, 370.
(14) For application of AgNO3 to palladium-catalyzed arylation
of vinylsilanes, see: (a) Karabelas, K.; Hallberg, A. J. Org.
Chem. 1986, 51, 5286. (b) Karabelas, K.; Hallberg, A.
Tetrahedron Lett. 1985, 26, 3131. (c) Karabelas, K.;
Hallberg, A. J. Org. Chem. 1988, 53, 4909.
(15) Oxford Diffraction(2007). CrysAlis CCD (Version
1.171.32.5) and CrysAlis RED (Version 1.171.32.5). Oxford
Diffraction Ltd.
Colorless oil; yield: 0.86 g (68%).
1H NMR (CDCl3): d = –0.20 (s, 9 H, SiCH3), –0.06 (s, 9 H, SiCH 3),
7.00–7.18 (m, 3 H, Ar), 7.21 (s, 1 H, =CH).
13C NMR (CDCl3): d = –0.3 (SiCH3), 0.7 (SiCH3), 123.7, 124.3,
127.8 (Ar), 144.4 (CH=), 147.9 (C=).
MS (EI): m/z (%) = 254 ([M]+, 25), 239 (100), 181 (25), 165 (10),
151 (10), 141 (50), 73 (50).
HRMS: m/z [M]+ calcd for C12H22Si2S: 254.0980; found: 254.0992.
X-ray Crystal Structure Analysis
Compound 2j: CCDC 640132; formula C13H23NSi2, Mr = 249.50,
crystal 0.1 × 0.1 × 0.3 mm from hexane soln, triclinic, space group
P1, a = 9.1811(7) Å, b = 11.8067(14) Å, c = 15.1746(9) Å,
a = 85.300(7)°, b = 78.733(6)°, g = 79.160(8)°, V = 1582.7(2) Å3,
r
calcd = 1.05
l(MoKa) = 0.71073 Å,
g
cm–3,
m = 0.20
mm–1,
reflections
Z = 4,
r.t.,
19419
collected
(Qmax = 27.95°), 6885 unique (Rint = 0.024), R(F) [I
>
2s(I)] = 0.042, wR(F2) = 0.147, S = 1.1–, max/min residual elec-
tron density 0.23/–0.23 e·Å–3. Oxford Diffraction four-circle dif-
fractometer equipped with CCD detector.15 The structures were
solved by direct methods with SHELXS9716 and refined by full-ma-
trix least squares with SHELXL97.16 Non-hydrogen atoms were re-
fined anisotropically, hydrogen atoms were located from the ideal
(16) Sheldrick, G. M. Acta Crystallogr., Sect. A 2008, 64, 112.
Synthesis 2009, No. 22, 3843–3847 © Thieme Stuttgart · New York