166
J. Beckmann et al. / Journal of Organometallic Chemistry 694 (2009) 161–166
4. The product is a colourless oil. Yield 13.85 g, 31.1 mmol, 76%.
Supplementary material
[
a
]D: ꢁ2.4 (c = 0.84, CHCl3). Anal. Calc. for C22H27ClSn (445.62): C,
59.30; H, 6.11. Found: C, 59.49; H, 6.01%.
CCDC 702006, 702007, 702008, 702009 and 702010 contain the
supplementary crystallographic data for 1, 3, 6, 7 and 8a. These
data can be obtained free of charge from The Cambridge Crystallo-
Synthesis of cis-myrtanylphenyltin dichloride (5) and trans-myrta-
nylphenyltin dichloride (6). A solution of the appropriate myrtanyl-
triphenyltin (15.00 g, 30.8 mmol) in CH2Cl2 (100 mL) was cooled at
0 °C and iodine (15.31 g, 60.3 mmol) added in small portions. The
solvent and iodobenzene were removed under reduced pressure.
The remainder was dissolved in Et2O (70 mL) and stirred with a
saturated solution of NH4Cl (3 ꢂ 40 mL) for 1 h. The organic layer
was washed with water (3 ꢂ 50 mL) and dried over Na2SO4. The
removal of the solvent provided the desired product that was sub-
ject to Kugelrohr distillation (200 °C/10ꢁ2 mbar).
Acknowledgements
Mrs. Irene Brüdgam (Freie Universität Berlin) is thanked for the
X-ray data collection. The Deutsche Forschungsgemeinschaft (DFG)
is gratefully acknowledged for financial support.
5. Recrystallization from CH2Cl2/hexane gave a colourless solid.
References
Yield 10.49 g, 26.0 mmol, 84%. M.p. 59 °C. [
a
]D: ꢁ23.1 (c = 1.00,
CHCl3). Anal. Calc. for C16H22Cl2Sn (403.97): C, 47.57; H, 5.49.
[1] (a) H. Schumann, B.C. Wassermann, J. Organomet. Chem. 365 (1989) C1;
(b) H. Schumann, B.C. Wassermann, F.E. Hahn, Organometallics 11 (1992)
2803;
Found: C, 47.00; H, 5.46%.
6. Colourless crystals from the melt. Yield 9.91 g, 24.5 mmol,
(c) G.E. Radivoy, J.C. Podestá, Organometallics 13 (1994) 3364;
(d) J.C. Podestá, A.B. Chopa, G.E. Radivoy, C.A. Vitale, J. Organomet. Chem. 494
(1995) 11;
(e) J.C. Podestá, C.A. Vitale, J. Chem. Soc., Perkin Trans. 1 (1996) 2407;
(f) C. Lucas, C.C. Santini, M. Prinz, M.-A. Cordonnier, J.-M. Basset, M.-F. Connil,
B. Jousseaume, J. Organomet. Chem. 520 (1996) 101;
(g) D. Dakternieks, K. Dunn, D.J. Henry, C.H. Schiesser, E.R.T. Tiekink,
Organometallics 18 (1999) 3342;
(h) D. Dakternieks, K. Dunn, B.R. Vincent, E.R.T. Tiekink, Main Group Met.
Chem. 23 (2000) 329;
(i) J. Beckmann, D. Dakternieks, A. Duthie, Organometallics 24 (2005) 773;
(j) M.B. Faraoni, A.D. Ayala, V. Vetere, M.L. Casella, O.A. Ferretti, J.C. Podesta,
Appl. Organomet. Chem. 19 (2005) 465.
80%. M.p. 47 °C.
[
a
]D: ꢁ0.6 (c = 1.73, CHCl3). Anal. Calc. for
C16H22Cl2Sn (403.97): C, 47.57; H, 5.49. Found: C, 47.21; H, 5.19%.
Synthesis of cis-myrtanyltin trichloride (7) and trans-myrtanyltin
trichloride (8). The appropriate myrtanyltriphenyltin (5.00 g,
10.3 mmol) was suspended in conc. HCl (100 mL) and refluxed
for 48 h. The crude product was extracted with CH2Cl2 (70 mL)
and dried over Na2SO4. The solvent was removed under reduced
pressure.
7. Recrystallization from hexane gave colourless crystals. Yield
3.42 g, 9.4 mmol, 92%. M.p. 88 °C. [
Anal. Calc. for C10H17Cl3Sn (362.31): C, 33.15; H, 4.73. Found: C,
33.07; H, 4.79%.
a]D: ꢁ31.5 (c = 0.71, CHCl3).
[2] S.D. Mandolesi, L.C. Koll, J.C. Podestá, J. Organomet. Chem. 587 (1999) 74.
[3] D. Dakternieks, K. Dunn, T.V. Perchyonok, C.H. Schiesser, Chem. Commun.
(1999) 1665.
[4] J. Beckmann, D. Dakternieks, M. Dräger, A. Duthie, Angew. Chem., Int. Ed. 118
(2006) 6509.
[5] (a) M. Andrianome, B. Delmond, Tetrahedron Lett. 26 (1985) 6341;
(b) M. Andrianome, B. Delmond, J. Chem. Soc., Chem. Commun. 17 (1985)
1203;
8. The product is a colourless oil. Yield 3.15 g, 8.7 mmol, 85%.
[a]D: +5.9 (c = 1.73, CHCl3). Anal. Calc. for C10H17Cl3Sn (362.31):
C, 33.15; H, 4.73. Found: C, 32.95; H, 4.73%.
8a. The colourless crystalline hydrolysis product [trans-MyrSn-
(OH)Cl2 ꢀ H2O]2 was obtained in an attempt to recrystallize 8 from
(c) R. Krishnamurti, H.G. Kuivila, J. Org. Chem. 51 (1986) 4947;
(d) M. Helliwell, E.J. Thomas, L.A. Townsend, J. Chem. Soc., Perkin Trans. 1 10
(2002) 1286.
hexane at aerobic conditions. M.p. 83 °C. [a]D: +7.2 (c = 0.85,
CHCl3). IR (KBr):
C20H40Cl4O4Sn2 (723.77): C, 33.19; H, 7.77. Found: C, 32.79; H,
m
(OH): 3473shd, 3381vs cmꢁ1. Anal. Calc. for
[6] J. Beckmann, A. Duthie, M. Grassmann, A. Semisch, Organometallics 27 (2008)
1495.
[7] I. Shiihara, J. Iyoda, J. Org. Chem. 35 (1970) 4267.
[8] (a) J.C. Braun, G.S. Fisher, Tetrahedron Lett. 21 (1960) 9;
(b) H.C. Brown, G. Zweifel, J. Am. Chem. Soc. 83 (1961) 2544;
(c) G. Zweifel, H.C. Brown, J. Am. Chem. Soc. 86 (1964) 393.
[9] A. Marinetti, F.-X. Buzin, L. Ricard, J. Org. Chem. 62 (1997) 297.
[10] B. Zobel, A.E.K. Lim, K. Dunn, D. Dakternieks, Organometallics 18 (1999) 4889.
[11] (a) C. Lecomte, J. Protas, M. Devaud, Acta Crystallogr. B 32 (1976) 923;
(b) R.R. Holmes, S. Shafieezad, V. Chandrasekhar, J.M. Holmes, R.O. Day, J. Am.
Chem. Soc. 110 (1988) 1174;
(c) H. Puff, H. Reuter, J. Organomet. Chem. 364 (1989) 57.
[12] (a) D. Dakternieks, K. Jurkschat, E.R.T. Tiekink, Main Group Met. Chem. 17
(1994) 471;
(b) A.G. Davies, Organotin Chemistry, Wiley-VCH, Weinheim, 2004.
[13] G. Dupont, W. Zacharewicz, Compl. Rend. 199 (1934) 365.
[14] For the complete assignment of 1H and 13C NMR signals of cis- and trans-
myrtanol, also see: K.-Y. Kim, S.-G. Lee, Magn. Reson. Chem. 35 (1997) 451.
5.09%.
X-ray crystallography. Intensity data were collected on a Bruker
SMART 1000 area detector with graphite-monochromated Mo K
a
(0.7107 Å) radiation. Data were reduced and corrected for absorp-
tion using the programs SAINT and SADABS [15]. The structures were
solved by direct methods and difference Fourier synthesis using
SHELXS-97 implemented in the program WINGX 2002 [16]. Full-matrix
least-squares refinements on F2, using all data. All non-hydrogen
atoms were refined using anisotropic displacement parameters.
Hydrogen atoms attached to carbon atoms were included in geo-
metrically calculated positions using a riding model and were re-
fined isotropically. For 8a, the hydrogen atoms attached to
oxygen atoms was located during the refinement and was also re-
fined isotropically. Crystal and refinement details are collected in
Table 2. Figures were created using DIAMOND [17].
[15] SMART, SAINT and SADABS, Siemens Analytical X-ray Instruments Inc., Madison,
Wisconsin USA, 1999.
[16] L.J. Farrugia, J. Appl. Cryst. 32 (1999) 837.
[17] K. Brandenburg, H. Putz, DIAMOND V3.1d, Crystal Impact GbR, 2006.