radial chromatography (light petroleum–dichloromethane
(1:1) elution) of the orange solid gave the title compound 9l
as dark orange needles (light petroleum) (22 mg, 18%), mp
176.0–177.5 °C (Found: C, 82.20; H, 4.13; N, 4.09. C24H15NO2
requires C, 82.50; H, 4.32; N, 4.01%). IR mmax/cm−1 2927, 2857,
1773 (w), 1731 (w), 1635, 1586, 1449, 1341, 1115, 1032, 963,
857, 698. UV kmax (cyclohexane)/nm 208 (4.21), 228 (4.19), 432
(log e 3.07); kmax (acetonitrile)/nm 210 (4.16), 238 (4.22), 436
References
1 B. Halton, C. J. Randall, G. J. Gainsford and P. J. Stang, J. Am.
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4 B. Halton and P. J. Stang, Synlett, 1997, 145.
5 B. Halton, C. J. Randall and P. J. Stang, J. Am. Chem. Soc., 1984,
106, 6108.
3
4
(log e 3.23). dH (300 MHz; CDCl3) 7.41 (tt, JAB 7.3, JAC 1.6,
1H, H18), 7.48–7.56 (m, 4H, H4/5 and H17/19), 7.69–7.73 (m,
4H, H2/7 and H16/20), 7.91–7.98 (m, 4H, H3/6 and H10/14),
6 Y. Apeloig, R. Boese, D. Bläser, B. Halton and A. H. Maulitz, J. Am.
Chem. Soc., 1998, 120, 10147.
7 B. Halton, S. J. Buckland, Q. Lu, Q. Mei and P. J. Stang, J. Org.
Chem., 1988, 53, 2418.
8 B. Halton, Q. Lu and P. J. Stang, J. Chem. Soc., Chem. Commun.,
1988, 879.
9 B. Halton, Q. Lu and W. H. Melhuish, J. Photochem. Photobiol., A:
Chem., 1990, 52, 205.
10 B. Halton, C. S. Jones and D. Margetic, Tetrahedron, 2001, 57,
3529.
11 B. Halton, C. S. Jones, P. T. Northcote and R. Boese, Aust. J. Chem.,
1999, 52, 285.
3
8.31 (d, JAB 8.3, 2H, H11/13). dC (75 MHz; CDCl3) 108.5
(C2 or C7), 108.8 (C7 or C2), 115.0 (C1), 117.2 (C8), 123.9
(C11/13), 126.4 (C1a or C7a), 126.6 (C7a or C1a), 127.5 (C18),
128.0 (C17/19), 128.1 (C4/5), 128.2 (C16/20), 128.8 (C3/6),
129.0 (C10/14), 138.3 (C15), 139.2 (C2a or C6a), 139.3 (C6a or
C2a), 146.3 (C9), 146.5 (C12). m/z (70 eV) 350 (29, M + 1), 349
(100, M), 303 (45, M–NO2), 302 (88), 301 (25), 300 (49), 151
(12), 150 (14%). l (22 °C) 3.10 D.
12 B. Halton and C. S. Jones, Eur. J. Org. Chem., 2004, 138.
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19 B. Halton, Q. Lu and P. J. Stang, Aust. J. Chem., 1990, 43, 1277.
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idenecyclopropabenzenes—A Synergistic Relationship Between
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22 A. H. Maulitz, PhD Thesis, University of Essen, Germany,
1995.
Method V. Disilane 1 and p-nitrobenzophenone gave an
orange solid. Radial chromatography (light petroleum–dichloro-
methane (1:1) elution) gave from the most mobile fraction title
compound 9l as dark orange needles (light petroleum) (12 mg,
10%), identical to that obtained above.
1-[Aryl(phenyl)methylidene]-3,6-dimethoxy-1H-cyclopropa[b]-
naphthalenes 10
The compounds were prepared from disilane 22 and the relevant
ketone according to the specified method described above.
1-[(p-Trifluoromethylphenyl)phenylmethylidene]-3,6-dimethoxy
10j serves as a representative example:
1-[(p-Trifluoromethylphenyl)phenylmethylidene]-3,6-di-
methoxy-1H-cyclopropa[b]naphthalene 10j. Method II. The
most mobile fraction from radial chromatography (light
petroleum–dichloromethane (2:1) elution) of the yellow solid
gave the title compound 10j as yellow needles (light petro-
leum) (101 mg, 81%), mp 137.0–138.0 °C (Found: C, 74.83;
H, 4.29; F, 13.33. [M + H]+ 433.1412; C27H19F3O2 requires C,
74.99; H, 4.43; F, 13.18%; 433.1415). IR mmax/cm−1 2930, 2837,
2169, 1782, 1774(w), 1611, 1465, 1438, 1407, 1384, 1341, 1322,
1266, 1225, 1171, 1109, 1066, 1013, 861, 795, 764, 703. UV kmax
(cyclohexane)/nm 258 (4.05), 308 (4.02), 320 (4.06), 410 (4.15),
434 (log e 4.09); kmax (acetonitrile)/nm 252 (3.70), 322 (3.99), 410
(4.12), 432 (log e 4.09). dH (300 MHz; CDCl3) 3.98 (s, 3H, C3– or
C6–OMe), 3.99 (s, 3H, C6– or C3–OMe), 6.76 (s, 2H, H4/5),
7.38 (tt, 3JAB 7.4, 4JAC 1.6, 1H, H18), 7.45–7.50 (m, 2H, H17/19),
7.69–7.73 (m, 2H, H11/13), 7.76–7.80 (m, 2H, H16/20), 7.88 (d,
3JAB 8.3, 2H, H10/14), 8.05 (d, Jpara 1.7, 1H, H2 or H7), 8.07 (d,
Jpara 1.7, 1H, H7 or H2). dC (75 MHz; CDCl3) 55.9 (OMe), 102.8
(C2 or C7), 103.0 (C7 or C2), 104.6 (C4/5), 113.9 (C1), 116.8
23 B. Halton, R. Boese and G. M. Dixon, Tetrahedron Lett., 2004, 45,
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1
3
(C8), 124.4 (q, JCF 272, CF3), 125.3 (q, JCF 3, C11/13), 126.7
(C1a or C7a), 126.7(5) (C7a or C1a), 127.4 (C18), 127.9 (C10/
14), 128.1 (C16/20), 128.6 (C17/19), 128.6 (q, 2JCF 33, C12), 131.4
(C2a or C6a), 131.5 (C6a or C2a), 138.9 (C15), 143.2 (C9), 150.5
(C3/6). l (21 °C) 3.19 D.
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1-(1-Phenylethylidene)-1H-cyclopropa[b]naphthalene 11.
Method III. Disilane 1 and acetophenone gave a yellow solid.
Radial chromatography (light petroleum elution) gave from the
most mobile fraction title compound 11 as yellow needles (light
petroleum) (72 mg, 85%), mp 94–95 °C (lit.1 39%, 94–95 °C).
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Acknowledgements
We are grateful to Victoria University and its former Science
Faculty Research fund administrators for financial support, and
to Dr. Daniel Pringle for generating the correlation diagrams of
Figs. 2 and 3.
3 1 4 8
O r g . B i o m o l . C h e m . , 2 0 0 4 , 2 , 3 1 3 9 – 3 1 4 9