E. Banaszak et al. / Tetrahedron 65 (2009) 3961–3966
3965
(cyclohexane/ethylacetate 9:1, Rf¼0.66). 1H NMR (200 MHz, CDCl3)
29.2, 29.1, 28.9, 28.7, 28.6, 28.4, 24.1, 22.1, 19.8, 0.16. IR (neat): 2931,
2855, 2174, 1464, 1101 cmꢁ1
d
: 3.40 (t, 2H, J¼7.0 Hz, CH2Br), 2.17 (t, 2H, J¼7.0 Hz, CH2C), 1.91 (q,
.
2H, J¼7.0 Hz, CH2CH2Br), 1.55–1.26 (m, 22H, CH2), 0.14 (s, 9H, TMS).
13C NMR (100 MHz, CDCl3)
d: 107.7, 84.1, 33.9, 32.8, 29.56, 29.52,
4.5.4. Trichloro[16-(trimethylsilyl)hexadec-15-ynyl]silane (2d)
According to the general procedure, (16-bromohexadec-1-ynyl)-
trimethylsilane (9d, 0.86 g, 2.30 mmol) afforded 2d (0.52 g, 53%) as
a colorless oil: bp 175–185 ꢀC (0.4 mbar). 1H NMR (400 MHz, CDCl3)
29.47, 29.42, 29.0, 28.9, 28.7, 28.6, 28.4, 28.1, 19.8, 0.17. HRMS (ESI),
calcd: 372.1848. Found: 372.1849. IR (neat): 2925, 2852, 2174, 1464,
1248 cmꢁ1. Anal. Calcd for C19H37BrSi: C, 61.10; H, 9.99. Found: C,
60.95; H, 10.01.
d
: 2.21 (t, 2H, J¼6.9 Hz, CH2C), 1.52 (q, 2H, J¼6.9 Hz, CH2CH2C), 1.47–
1.28 (m, 24H, CH2), 0.14 (s, 9H, TMS). 13C NMR (100 MHz, CDCl3)
107.5, 84.0, 31.9, 30.3, 29.2, 29.1, 28.9, 28.8, 28.7, 28.6, 28.4, 24.1, 22.1,
19.3, 0.3. IR (neat): 2936, 2852, 2175, 1466, 1080 cmꢁ1
d
:
4.4.5. (18-Bromooctadec-1-ynyl)trimethylsilane (9e)
(Trimethylsilyl)octadec-17-yn-1-ol (10e, 1.10 g, 3.25 mmol) was
dissolved in DCM (20 mL) and treated successively with PPh3
(1.28 mg, 4.87 mmol) in DCM (5 mL) and CBr4 (1.62 g, 4.87 mmol)
in DCM (5 mL). After evaporation of the solvent and chromatogra-
phy (hexane/ethylacetate 25:1), 9e was isolated as a pale yellow oil
(1.23 g, 95%) (cyclohexane/ethylacetate 9:1, Rf¼0.71). 1H NMR
.
4.5.5. Trichloro[18-(trimethylsilyl)octadec-17-ynyl]silane (2e)
According to the general procedure, (18-bromooctadec-1-ynyl)-
trimethylsilane (9e, 0.924 g, 2.30 mmol) afforded 2e (0.61 g, 58%) as
a yellow oil: bp 190–200 ꢀC (0.08 mbar). 1H NMR (400 MHz, CDCl3)
(200 MHz, CDCl3)
J¼6.9 Hz, CH2C), 1.85 (q, 2H, J¼6.9 Hz, CH2CH2Br), 1.56–1.25 (m,
26H, CH2), 0.14 (s, 9H, TMS). 13C NMR (100 MHz, CDCl3)
: 107.7,
d
: 3.40 (t, 2H, J¼6.9 Hz, CH2Br), 2.20 (t, 2H,
d
: 2.21 (t, 2H, J¼6.9 Hz, CH2C), 1.52 (q, 2H, J¼6.9 Hz, CH2CH2C), 1.47–
1.28 (m, 28H, CH2), 0.14 (s, 9H, TMS). 13C NMR (100 MHz, CDCl3)
d:
d
107.6, 84.0, 33.8, 33.7, 31.9, 30.3, 29.2, 29.1, 28.9, 28.8, 28.7, 28.6,
28.4, 24.1, 22.1, 19.3, 0.3. IR (neat): 2933, 2854, 2175, 1464,
84.1, 33.9, 32.8, 29.6, 29.5, 29.5, 29.4, 29.0, 28.7, 28.7, 28.6, 28.4, 28.1,
19.8, 0.18. MS (EI): 328 [MꢁSiMe3]þ. IR (neat): 2925, 2852, 2174,
1093 cmꢁ1
Acknowledgements
This research was supported by CNRS and Universite du Maine.
.
1464, 1248 cmꢁ1
.
4.5. Preparation of trichloro[(trimethylsilyl)alkynyl]-
silanes (2a–e)
´
´
E.B. and L.-W.X. would like to thank CNRS and Region Pays-de-la-
The glassware was dried with a heat gun at w500 ꢀC for 3 h
Loire (France) for postdoctoral fellowships. We express apprecia-
under vacuum prior to use, and the Mg was dried in an oven
´
tion to our colleagues at Universite du Maine for contributions to
overnight. In a flask flushed with argon were combined the (u-
this work: Patricia Gangnery (mass spectra) and Martine Jean (NMR
studies).
bromoalk-1-ynyl)trimethylsilanes 9a–e (2.3 mmol), metallic mag-
nesium (223 mg, 9.25 mmol of finely shredded turnings), and
10 mL of THF. The mixture was allowed to react at rt for 3–4 h
during which the color of the solution changed from light yellow to
clear black. The Grignard was transferred into a flask containing
SiCl4 (1.1 mL, 9.2 mmol) in dry THF (5 mL) under argon. The
resulting mixture was stirred overnight at rt. The solvent and re-
sidual SiCl4 were removed by a trap-to-trap distillation and the
residue was triturated under argon with anhydrous cyclohexane.
The supernatant solution was transferred via cannula into a dry
flask connected to a cold trap. Concentration in vacuo followed by
bulb-to-bulb distillation afforded 2a–e.
References and notes
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Science 2003, 299, 371–374; (d) Flink, S.; Veggel, F. C. J. M. V.; Reinhoudt, D. N.
Adv. Mater. 2000, 12, 1315–1328; (e) Basabe-Desmonts, L.; Beld, J.; Zimmerman,
R. S.; Hernando, J.; Mela, P.; Parajo, M. F. G.; Van Hulst, N. F.; Berg, A. V. D.;
Reinhouldt, D. N.; Crego-Calama, M. J. Am. Chem. Soc. 2004, 126, 7293–7299.
3. (a) Netzer, L.; Isocovici, R.; Sagiv, J. Thin Solid Films 1983, 99, 235–241; (b)
Wasserman, S. R.; Tao, Y. T.; Whitesides, G. M. Langmuir 1989, 5, 1074–1087; (c)
Hamelmann, F.; Heinzmann, U.; Siemeling, U.; Bretthauer, F.; vor der Briiggen, J.
Appl. Sur. Sci. 2004, 222, 1–5; (d) Killampalli, A. S.; Ma, P. F.; Engstrom, J. R. J. Am.
Chem. Soc. 2005, 127, 6300–6310.
4. Bennetau, B.; Bousbaa, J.; Choplin, F. Wo. Pat. Appl. WO 01/53303A1, 2001.
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Gibaud, A.; Mortier, J. Tetrahedron 2006, 62, 647–651.
6. Peanaski, J.; Schneider, H.; Granick, S.; Kessel, C. Langmuir 1995, 11, 953–962.
7. Recent review: (a) Meldal, M.; Wenzel Tornøe, C. Chem. Rev. 2008, 108, 2952–
3015; See also: (b) Kolb, H. C.; Finn, M. G.; Sharpless, K. B. Angew. Chem., Int. Ed.
2001, 40, 2004–2021; (c) Golas, P. L.; Matyjaszewski, K. QSAR Comb. Sci. 2007,
26, 1116–1134.
4.5.1. Trichloro[10-(trimethylsilyl)dec-9-ynyl]silane (2a)
According to the general procedure, (10-bromodec-1-ynyl)-
trimethylsilane (9a, 662 mg, 2.3 mmol) afforded 2a (0.41 g, 52%) as
a yellow oil: bp 110–125 ꢀC (0.08 mbar). 1H NMR (200 MHz, CDCl3)
d
: 2.21 (t, 2H, J¼7.0 Hz, CH2C), 1.64–1.32 (m, 14H, CH2), 0.15 (s, 9H,
TMS). 13C NMR (100 MHz, CDCl3)
: 107.4, 84.2, 31.6, 28.7, 28.6, 28.5,
28.4, 24.1, 22.1, 19.6, 0.15. IR (neat): 2932, 2854, 2174, 1464,
1093 cmꢁ1
d
.
8. Nishihara, Y.; Takemura, M.; Mori, A.; Osakada, K. J. Organomet. Chem. 2001,
620, 282–286.
4.5.2. Trichloro[12-(trimethylsilyl)dodec-11-ynyl]silane (2b)
According to the general procedure, (12-bromododec-1-ynyl)-
trimethylsilane (9b, 0.72 g, 2.30 mmol) afforded 2b (0.49 g, 57%) as
a colorless oil: bp 175–190 ꢀC (0.4 mbar). 1H NMR (400 MHz, CDCl3)
9. Hosomi and Mori reported that CuCl and CuCl–Pd(PPh3)4 are efficient catalysts
for cross-coupling reactions of phenyltrimethylsilylacetylene with acyl chlo-
rides and aryl triflates, respectively. Both reactions presumably involve CuCl
promoted Si–C(sp) bond cleavage of the alkynylsilane to form an alkynylcopper
species with high reactivity toward coupling with the electrophiles and
transmetalation giving an alkynylpalladium species leads to the smooth cata-
lytic reactions. See: (a) Ito, H.; Arimoto, K.; Sensui, H.; Hosomi, A. Tetrahedron
Lett. 1997, 38, 3977–3980; (b) Nishihara, Y.; Ikegashira, K.; Hirabayashi, K.;
Ando, J.; Mori, A.; Hiyama, T. J. Org. Chem. 2000, 65, 1780–1787.
d
: 2.21 (t, 2H, J¼6.9 Hz, CH2C), 1.52 (q, 2H, J¼6.9 Hz, CH2CH2C), 1.47–
1.28 (m, 16H, CH2), 0.14 (s, 9H, TMS). 13C NMR (100 MHz, CDCl3)
107.7, 84.2, 31.9, 28.7, 28.6, 28.5, 28.4, 24.1, 22.1, 19.8, 0.16. IR (neat):
2925, 2852, 2174, 1464, 1048 cmꢁ1
d:
.
10. (a) Ogawa, K.; Mino, N.; Tamura, H.; Hatada, M. Langmuir 1990, 6, 1807–1809;
(b) Tamura, H.; Ogawa, K. Eur. Pat. Appl. EP 351092, 1990; (c) Ogawa, K. Eur. Pat.
Appl. EP 339677, 1989.
4.5.3. Trichloro[13-(trimethylsilyl)tridec-12-ynyl]silane (2c)
According to the general procedure, (13-bromotridec-1-ynyl)-
trimethylsilane (9c, 0.76 g, 2.30 mmol) afforded 2c (0.54 g, 61%) as
a colorless oil: bp 160–180 ꢀC (0.08 mbar). 1H NMR (200 MHz,
11. Trichloro[u-(trimethylsilyl)alkynyl]silanes with an odd number of carbons are
comparatively more expensive to produce since relatively expensive reactants
are required to obtain the same.
12. Chong, J. M.; Heuft, M. A.; Rabbat, P. J. Org. Chem. 2000, 65, 5837–5838.
13. Rodriguez, A.; Nomen, M.; Spur, B. W.; Godfroid, J. J. Tetrahedron Lett. 1998, 39,
8563–8566.
CDCl3)
d
: 2.21 (t, 2H, J¼6.9 Hz, CH2C), 1.63–1.28 (m, 20H, CH2), 0.14
(s, 9H, TMS). 13C NMR (100 MHz, CDCl3)
d
: 107.6, 84.1, 31.6, 29.3,