9-(1-Indenyl)triptycene (1) and 10-(anthracen-9ꢀ-yl)-
[4a,9]-methano-4a,9-dihydro-phenanthrene (16)
H1), 7.74 (1H, pseudo-t, H7, J 8.0), 7.68 (1H, pseudo-t, H6, J 8.0),
7.67 (1H, d, H12, J 8.0), 7.63 (2H, m, H2, H3), 7.49 (1H, pseudo-t,
H10, J 8), 7.35 (1H, pseudo-t, H11, J 8.0), 4.23 (CH2, s, H13); dC
(125 MHz, CDCl3): 142.8 (C8c), 142.2 (C12a), 139.0 (C13a), 133.6
(C8b), 129.9 (C4b), 128.9 (C4a), 128.7 (C13b), 128.3 (C8a), 126.0 (C2),
126.0 (C7), 126.0 (C10), 125.5 (C3), 124.9 (C6), 124.7 (C11), 123.8
(C12), 123.7 (C1), 123.5 (C8), 122.7 (C5), 122.4 (C4), 36.8 (C13). 22
as a white solid (Found: C, 93.80; H, 6.15. C27H20 requires: C,
94.15; H, 5.85); mp 145 ◦C; dH (500 MHz, CDCl3, numbering in
accord with Scheme 7) 7.84 (1H, d, H4, J 9.2), 7.74 (1H, d, H5, J
9.2), 7.56 (1H, d, H8, J 7.6), 7.40 (1H, d, H1, J 8.8), 7.37 (2H, m,
H2,3), 7.27 (2H, d, H15,19, J 7.2), 7.20–7.10 (6H, m, H7, H6, H9, H16,
H18, H17) 7.06 (1H, pseudo-t, H10, J 7.8), 7.00 (1H, pseudo-t, H11,
J 7.6), 6.82 (1H, d, H12, J 7.6), 4.04 and 3.85 (CH2, each 1H, d,
H14, J 15.2); dC (125 MHz, CDCl3): 146.9 (C19a), 144.5 (C12a), 141.1
(C12b), 139.8 (C8a), 134.8 (C13b), 133.4 (C4b), 132.9 (C4a), 129.8 (C1),
128.3 (C16,18), 128.1 (C8), 127.7 (C2,3), 127.0 (C6), 126.8 (C10), 126.6
(C15,19), 126.5 (C11), 126.3 (C17), 124.2 (C4), 123.6 (C5), 123.5 (C12),
123.5 (C9), 56.6 (C13a), 56.4 (C13), 46.2 (C14).
To a hot (80 ◦C) stirred solution of 3 (292 mg, 1 mmol) and
isopentyl nitrite (380 mg, 3.2 mmol) in dichloroethane (6 mL)
was added a solution of anthranilic acid (440 mg, 3.2 mmol) in
dioxane (2.5 mL) over a period of 30 min. The reaction mixture was
extracted with dichloromethane and separated by chromatography
eluting with 5% dichloromethane in cyclohexane to give 3 (82 mg,
28%), 16 (42 mg, 11%) and the triptycene 1 (156 mg, 42%).7 The
adduct 16 as a yellow solid (Found C, 94.11; H, 5.51. C29H20
requires C, 94.53; H, 5.47); mp 155 ◦C; dH (500 MHz, CDCl3,
numbering in accord with Fig. 3): 8.41 (1H, s, H16), 8.24 (1H, d,
H12, J 9.9), 8.06 (1H, d, H15, J 9.6), 7.92 (1H, d, 1H, H17, J 8.8),
7.52 (2H, m, H14, H13), 7.31 (1H, pseudo-t, H18, J 7.6), 7.23 (1H,
d, H5, J 6.7), 7.12 (1H, pseudo-t, H6, J 6.8), 7.11 (1H, d, H8, J
7.2), 7.03 (1H, pseudo-t, H7, J 7.2), 6.95 (1H, ddd, H19, J 9.2, 6.5,
1.6), 6.62 (1H, d, H4, J 9.5), 6.55 (1H, dd, H3, J 9.5 and 6.5), 6.45
(1H, d, H20, J 9.2), 6.05 (1H, dd, H2, J 9.2 and 5.2), 5.95 (1H, d,
H1, J 9.2), 4.46 (1H, s, H9), 2.94 and 2.89 (CH2, each d, 1H, H11, J
7.2); dC (CDCl3, 125 MHz): 156.2 (C4b), 149.6 (C10a), 145.9 (C8a),
144.7 (C10), 131.9 (C20b), 131.7 (C16a), 131.5 (C15a), 130.6 (C4), 130.2
(C20c), 129.4 (C20a), 128.7 (C15), 128.1 (C17), 126.8 (C3), 126.4 (C16),
126.3 (C20), 125.6 (C7), 125.5 (C14), 125.2 (C13), 125.1 (C18), 125.1
(C19), 124.8 (C8), 124.1 (C2), 123.4 (C6), 121.4 (C5), 121.4 (C1), 78.5
(C11), 60.6 (C4a), 57.9 (C9).
Crystal data
Crystallographic data were collected using a Bruker SMART
APEX CCD area detector diffractometer. A full sphere of the
reciprocal space was scanned by phi-omega scans. A semi-
empirical absorption correction, based on redundant reflections,
was performed by the program SADABS.31a The structures were
solved by direct methods and refined by full-matrix least-squares
on F2 for all data using the program library SHELXTL.31b,c In
16, all hydrogen atoms were located in the difference Fourier map
and allowed to refine freely. In 2 and 7a, all hydrogen atoms were
added at calculated positions and refined using a riding model.
Their isotropic temperature factors were fixed to 1.2 times the
equivalent isotropic displacement parameters of the carbon atom
the H-atom is attached to.†
9-(2-Indenyl)triptycene (2)
To a hot stirred solution of 4 (117 mg, 0.4 mmol) and isopentyl
nitrite (187 mg, 1.6 mmol) in dichloroethane (3 mL) was added a
solution of anthranilic acid (205 mg, 1.5 mmol) in dioxane (1 mL)
over a period of 30 min. The reaction mixture was extracted with
dichloromethane and separated by chromatography eluting with
5% dichloromethane in cyclohexane to give starting 4 (14 mg,
12%), and triptycene 2 (120 mg, 81%) as a white solid (Found C,
94.25; H, 5.59. C29H20 requires: C, 94.53; H, 5.47); mp 308 ◦C; dH
(500 MHz, CD2Cl2, numbering in accord with Fig. 4): 7.70 (1H,
d, H22, J 7.5), 7.62 (1H, d, H19, J 7.5), 7.56 (3H, d, H4,5,16, J 6.9),
7.49 (3H, d, H1,8,13, J 7.5), 7.48 (1H, s, H18), 7.45 (1H, pseudo-t,
H20, J 7.5), 7.37 (1H, pseudo-t, H21, J 7.5), 7.08 (3H, pseudo-t,
H2,7,14, J 7.5), 7.04 (3H, pseudo-t, H3,6,15, J 7.0), 5.48 (1H, s, H10),
4.36 (CH2, s, H23); dC (125 MHz, CD2Cl2): 146.9 (C4a,10a,11), 146.4
(C8a,9a,12), 143.9 (C18a), 143.3 (C17), 143.3 (C22a), 136.1 (C18), 126.6
(C20), 125.3 (C2,7,14), 125.0 (C21), 124.8 (C3,6,15), 123.8 (C4,5,16), 121.1
(C19), 59.0 (C9), 54.8 (C10), 42.9 (C23).
Acknowledgements
We thank Science Foundation Ireland and University College
Dublin for generous financial support.
References
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13a-Phenyl-13,13a-dihydro-8bH-indeno-[1,2-l]-phenanthrene (22),
and 13H-indeno[1,2-l]-phenanthrene (21)
To a hot stirred solution of 8 (96 mg, 0.5 mmol) and isopentyl
nitrite (234 mg, 2 mmol) in dichloroethane (4 mL) was added a
solution of anthranilic acid (274 mg, 2 mmol) in dioxane (1.5 mL)
over a period of 30 min. The reaction mixture was extracted with
dichloromethane and separated eluting with 3% dichloromethane
in cyclohexane to give 8 (84 mg, 88%), 21 (5 mg, 3.7%) and 22
(10 mg, 6%); 21 as a white solid (Found C, 94.54; H, 5.40. C21H14
◦
requires: C, 94.70; H, 5.30); mp 158 C;27 dH (500 MHz, CDCl3,
† CCDC reference numbers 638735–638737 for the compounds 7a, 16 and
2 respectively. For crystallographic data in CIF or other electronic format
see DOI: 10.1039/b703437g
numbering in accord with Scheme 7) 8.85 (1H, d, H8, J 8.0), 8.79
(1H, d, H5, J 8.2), 8.75 (1H, m), 8.39 (1H, d, H9, J 7.8), 8.07 (1H, m,
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