110
G. Dyker et al. / Journal of Organometallic Chemistry 606 (2000) 108–111
4. Supplementary material
hexanes–ethyl acetate). First fraction (Rf=0.39): 90
mg (70%) recovered starting material 1. Second frac-
tion (Rf=0.14): 40 mg (16%) green crystals of 3b
with m.p. 94–96°C. Selected spectroscopic data of 3b:
UV (acetonitrile): umax (l g m)=232 nm (4.45), 284
The crystallographic data (without structure fac-
tors) have been deposited as supplementary publica-
tion
no.
CCDC-139097
at
the
Cambridge
1
Crystallographic Data Centre. Copies of the data may
be obtained free of charge from The Director,
CCDC, 12 Union Road, Cambridge CB2 1EZ, UK
(Fax: +44-1223-336033; e-mail: deposit@ccdc.cam.
ac.uk or www: http://www.ccdc.cam.ac.uk)
(4.53), 335 (3.94, sh), 407 (4.20). H-NMR (500 MHz,
CDCl3, TMS): l=7.28 ppm (t, J=10 Hz, 2H, 5-H,
7-H), 7.47 (d, J=4.0 Hz, 1H, 3-H), 7.69 (t, J=10
Hz, 1H, 6H), 7.76 (d, J=9 Hz, 2H, 2%/6%-H), 8.06 (d,
J=4.0 Hz, 1H, 2-H), 8.34 (d, J=9 Hz, 2H, 3%/5%-H),
8.42 (d, J=9.3 Hz, 1H), 8.57 (d, J=10 Hz, 1H).
13C-NMR (125 MHz, CDCl3): l=118.33 ppm (d),
124.12 (d), 124.53 (d), 124.78 (d), 128.47 (s), 129.75
(d), 135.32 (d), 135.87 (s), 137.32 (d), 138.01 (d),
138.95 (d), 142.82 (s), 144.38 (s), 145.86 (s). MS (70
eV); m/z (%): 250 (19), 249 [100, M+], 219 (11), 204
(39), 202 (89), 201 (17), 200 (16), 101 (16), 88 (11).
Calc. for C16H11NO2 (259.27): C, 77.10; H, 4.45; N,
5.62. Found: C, 76.87; H, 4.53; N, 5.67%.
Acknowledgements
Financial support of the Fonds der Chemischen In-
dustrie and the Dr Otto Ro¨hm-Geda¨chtnisstiftung
and a generous donation of palladium acetate from
the Degussa AG is gratefully acknowledged.
Selected spectroscopic data of 1-phenylazulene (3a)
[20]: blue crystals with m.p. 53–54°C. H-NMR (500
1
References
MHz, CDCl3, TMS): l=7.14 ppm (t, J=10 Hz, 2H,
5-H, 7-H), 7.34 (t, J=7.4 Hz, 1H, 4%-H), 7.43 (d,
J=3.9 Hz, 1H, 3-H), 7.49 (t, J=7.5 Hz, 2H, 3%/5%-
H), 7.58 (t, J=9.9 Hz, 1H, 6-H), 7.62 (d, J=8.3 Hz,
2H, 2%/6%-H), 8.02 (d, J=3.6 Hz, 1H, 2-H), 8.34 (d,
J=8.8 Hz, 1H, 4-H), 8.55 (d, J=9.7 Hz, 1H, 8-H).
13C-NMR (125 MHz, CDCl3): l=117.48 ppm (d),
123.07 (d), 123.34 (d), 126.31 (d), 128.66 (d), 129.79
(d), 131.35 (s), 135.25 (s), 136.64 (d), 137.18 (d),
137.31 (d), 137.54 (s), 138.23 (d), 141.71 (s).
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Selected spectroscopic data of 1-benzylazulene: blue
crystals with m.p. 58–59°C. 1H-NMR (500 MHz,
CDCl3, TMS): l=4.45 ppm (s, 2H), 7.08 (t, J=9.8
Hz, 2H, 5-H, 7-H), 7.14–7.20 (m, 3H), 7.24 (d, J=
7.8 Hz, 2H), 7.33 (d, J=3.6 Hz, 1H, 3-H), 7.53 (t,
J=9.9 Hz, 1H, 6-H), 7.72 (d, J=3.6 Hz, 1H, 2-H),
8.26 (d, J=9.4 Hz, 1H), 8.29 (d, J=9.7 Hz, 1H).
13C-NMR (125 MHz, CDCl3): l=33.69 ppm (t),
116.88 (s), 121.81 (d), 122.42 (d), 125.84 (d), 128.40
(d), 128.59 (d), 129.11 (d), 133.64 (d), 135.93 (s),
136.55 (d), 137.48 (d), 138.05 (d), 140.84 (s), 141.90
(s).
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Selected spectroscopic data of 1,2%-biazulenyl: green
crystals with m.p. 140–141°C from pentane (lit. [21]
m.p. 144–145°C). 1H-NMR (500 MHz, CDCl3,
TMS): l=7.21–7.15 ppm (m, 3H), 7.27 (t, J=9.9
Hz, 1H), 7.49–7.45 (m, 2H), 7.63 (t, J=9.9 Hz, 1H),
7.75 (s, 2H), 8.29 (d, J=9.2 Hz, 2H), 8.34–8.33 (m,
2H), 9.06 (d, J=9.8 Hz, 1H). 13C-NMR (125 MHz,
CDCl3): l=116.50 ppm (d), 118.97 (d), 123.81 (d),
124.20 (d), 124.46 (d), 127.19 (s), 134.57 (d), 135.14
(d), 136.26 (d), 136.27 (s), 137.29 (d), 138.51 (d),
138.60 (d), 141.28 (s), 143.55 (s), 146.67 (s).
[10] T. Jeffery, Tetrahedron Lett. 26 (1985) 2667.
[11] G. Dyker, J. Org. Chem. 58 (1993) 234.
[12] Caesium carbonate did not facilitate the arylation in this case.
[13] W.A. Herrmann, C. Brossmer, C.-P. Reisinger, T.H. Riermeier,
8
K. Ofele, M. Beller, Chem. Eur. J. 3 (1997) 1357.
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1921.
[15] A related cross coupling reaction of a bromomethylindole with
1,2-dimethoxybenzene has recently been described: (a) W.G.
Rajeswaran, P.C. Srinivasan, Synthesis (1994) 270. (b) W.G.
Rajeswaran, P.C. Srinivasan, Synthesis (1992) 835.
[16] Our attempts to apply phenyl triflate in order to achieve aryla-
tion via cationic Pd-complexes were unsuccessful.