3640
C.-W. Huang et al. / Tetrahedron 59 (2003) 3635–3641
(d, J¼8.8 Hz, 2H), 6.16 (t, J¼6.8 Hz, 1H), 5.15 (d,
J¼6.8 Hz, 2H), 3.81 (s, 3H); 13C NMR: d 209.31, 158.66,
127.69, 126.04, 114.07, 93.29, 78.65, 55.17; MS (m/z): 146
(Mþ).
33.67, 26.67, 7.97; HRMS calcd for C9H10O 134.0732,
found 134.0728.
3.2.17. 3-(1,2-Propadienyl)-2-cyclohexen-1-one (7b).
1
Yellow oil; IR (neat) 1930, 1670, 1611, 802 ccm21; H
3.2.8. 1-Chloro-4-(1,2-propadienyl)benzene (3h).28
NMR: d 5.89 (t, J¼6.4 Hz, 1H), 5.82 (s, 1H), 5.06 (d, J¼
6.4 Hz, 2H), 2.32–2.28 (m, 4H), 1.95–1.88 (m, 2H); 13C
NMR: d 212.19, 199.15, 155.70, 125.69, 95.93, 78.82,
37.27, 25.99, 22.12; HRMS calcd for C9H10O 134.0732,
found 134.0728.
1
Colorless oil; H NMR: d 7.26 (d, J¼8.8 Hz, 2H), 7.20 (d,
J¼8.4 Hz, 2H), 6.11 (t, J¼6.4 Hz, 1H), 5.14 (d, J¼6.8 Hz,
2H); 13C NMR: d 209.81, 132.46, 128.73, 127.85, 93.11,
79.14; MS (m/z): 150 (Mþ).
3.2.9. 1-Bromo-4-(1,2-propadienyl)benzene (3i). Color-
less oil; 1H NMR: d 7.41 (d, J¼7.6 Hz, 2H), 7.14 (d,
J¼8.8 Hz, 2H), 6.10 (t, J¼6.8 Hz, 1H), 5.14 (d, J¼6.4 Hz,
2H); 13C NMR: d 209.75, 132.88, 131.62, 128.15, 120.46,
93.15, 79.21; HRMS calcd for C9H7Br 193.9731, found
193.9726.
3.2.18. 2-Methyl-3-(1,2-propadienyl)-2-cyclohexen-1-one
(7c). Yellow oil; IR (neat) 1928, 1658, 1599, 813 cm21; 1H
NMR: d 6.29 (t, J¼6.4 Hz, 1H), 5.07 (d, J¼6.8 Hz, 2H),
2.40–2.36 (m, 4H), 1.94–1.86 (m, 2H), 1.81 (s, 3H); 13C
NMR: d 212.39, 198.48, 147.70, 130.55, 93.23, 78.13,
37.55, 27.06, 21.80, 10.29; HRMS calcd for C10H12O
148.0888, found 148.0889.
3.2.10. 1-(4-(1,2-Propadienyl)phenyl)-1-ethanone (3j).
1
Colorless oil; H NMR: d 7.84 (d, J¼8.4 Hz, 2H), 7.31 (d,
J¼8.4 Hz, 2H), 6.15 (t, J¼6.8 Hz, 1H), 5.16 (d, J¼6.8 Hz,
2H), 2.53 (s, 3H); 13C NMR: d 210.63, 197.29, 139.13,
135.43, 128.66, 126.58, 93.46, 79.11, 26.37; HRMS calcd
for C11H10O 158.0732, found 158.0729.
Acknowledgements
We thank the National Science Council of the Republic of
China (NSC 91-2113-M-007-053) for support of this
research.
3.2.11. 1-Nitro-4-(1,2-propadienyl)benzene (3k).29 Color-
1
less solid, mp 638C; H NMR: d 8.10 (d, J¼8.8 Hz, 2H),
7.37 (d, J¼8.8 Hz, 2H), 6.19 (t, J¼6.4 Hz, 1H), 5.23 (d, J¼
6.4 Hz, 2H); 13C NMR: d 211.11, 146.37, 141.31, 126.99,
123.88, 92.99, 79.67; MS (m/z): 161 (Mþ).
References
1. For reviews, see: Brandsma, L.; Verkruijsse, H. D. Synthesis of
Acetylenes, Allenes and Cummulenes; Elsevier: New York,
1981.
3.2.12. 1-(1,2-Propadienyl)naphthalene (3l). Colorless
oil; 1H NMR: d 8.19 (d, J¼8.0 Hz, 1H), 7.84 (d, J¼
7.2 Hz, 1H), 7.73 (d, J¼8.4 Hz, 1H), 7.58 (d, J¼6.8 Hz,
1H), 7.52–7.41 (m, 3H), 6.85 (t, J¼6.8 Hz, 1H), 5.19 (d,
J¼6.8 Hz, 2H); 13C NMR: d 211.06, 133.95, 130.81,
130.15, 128.66, 127.46, 126.00, 125.69, 125.62, 125.33,
123.51, 90.44, 77.76; HRMS calcd for C13H10 166.0783,
found 166.0771MS.
2. For reviews, see: (a) Marshall, J. A. Chem. Rev. 1996, 96, 31.
(b) Yamamoto, Y.; Radhakrishnanan, U. Chem. Soc. Rev.
1999, 28, 199. (c) Zimmer, R.; Dinesh, C. U.; Nandanam, E.;
Khan, F. A. Chem. Rev. 2000, 100, 3067. (d) Marshall, J. A.
Chem. Rev. 2000, 100, 3163.
3. (a) Yang, F.-Y.; Cheng, C.-H. J. Am. Chem. Soc. 2001, 123,
761. (b) Jeganmohan, M.; Shanmugasundaram, M.; Chang,
K.-J.; Cheng, C.-H. Chem. Commun. 2002, 2552. (c) Onozawa,
S.-y.; Hatanaka, Y.; Tanaka, M. Chem. Commun. 1999, 1863.
(d) Suginome, M.; Ohmori, Y.; Ito, Y. Synlett 1999, 1567.
4. (a) Wu, M.-Y.; Yang, F.-Y.; Cheng, C.-H. J. Org. Chem. 1999,
64, 2471. (b) Yang, F.-Y.; Wu, M.-Y.; Cheng, C.-H. J. Am.
Chem. Soc. 2000, 122, 7122. (c) Huang, T.-H.; Chang, H.-M.;
Wu, M.-Y.; Cheng, C.-H. J. Org. Chem. 2002, 67, 99. (d) Tsuji,
J.; Shimizu, I. Chem. Lett. 1984, 233. (e) Chaptal, N.;
Colovray-Gotteland, V.; Grandjean, C.; Cazes, B.; Gore, J.
Tetrahedron Lett. 1991, 32, 1795.
3.2.13. 1-(1-Deuterio-1,2-propadienyl)benzene (5a).
Colorless oil; 1H NMR: d 7.33–7.23 (m, 5H), 5.17 (s,
1H); 13C NMR: d 209.78, 133.83, 128.58, 126.84, 126.64,
93.92, 93.69, 93.45, 78.82; HRMS calcd for C9H7D
117.0688, found 117.0692.
3.2.14. 1-(1,2-Butadienyl)benzene (5b).13c Colorless oil;
1H NMR: d 7.36–7.21 (m, 5H), 6.16 (m, 1H), 5.60 (m, 1H),
1.86–1.83 (m, 3H); 13C NMR: d 205.99, 135.02, 128.50,
126.62, 93.98, 89.52, 14.03; HRMS calcd for C10H10
130.07833, found 130.0746.
5. (a) Chang, H.-M.; Cheng, C.-H. Org. Lett. 2000, 2, 3439.
(b) Anwar, U.; Grigg, R.; Rasparini, M.; Savic, V.; Sridharan,
V. Chem. Commun. 2000, 645.
3.2.15. 1-(3-Phenyl-1,2-propadienyl)benzene (5c).30
Colorless solid, mp 538C; 1H NMR: d 7.36–7.21 (m,
10H), 6.58 (m, 2H); 13C NMR: d 207.79, 133.60, 128.73,
127.31, 126.99, 98.42; HRMS calcd for C15H12 192.0939,
found 192.0933.
6. (a) Shanmugasundaram, M.; Wu, M.-S.; Cheng, C.-H. Org.
Lett. 2001, 3, 4233. (b) Shanmugasundaram, M.; Wu, M.-S.;
Jeganmohan, M.; Huang, C.-W.; Cheng, C.-H. J. Org. Chem.
2002, 67, 7724.
7. (a) Alexakis, A.; Marek, I.; Mangeney, P.; Normant, J. F.
J. Am. Chem. Soc. 1990, 112, 8042. (b) Alexakis, A.; Marek,
II.; Mangeney, P.; Normant, J. F. Tetrahedron 1991, 47, 1677.
(c) Nantz, M. H.; Bender, D. M.; Janaki, S. Synthesis 1993,
577. (d) Myers, A. G.; Zheng, B. J. Am. Chem. Soc. 1996, 118,
4492.
3.2.16. 2-Methyl-3-(1,2-propadienyl)-2-cyclopenten-1-
one (7a). Yellow oil; IR (neat) 1928, 1668, 1614,
1
809 cm21; H NMR: d 6.29 (t, J¼6.4 Hz, 1H), 5.12 (d,
J¼6.4 Hz, 2H), 2.51 (m, 2H), 2.34 (m, 2H), 1.71 (s, 3H); 13C
NMR: d 212.68, 208.94, 161.74, 136.06, 89.96, 78.24,