LETTER
Synthesis of 2-Substituted Cyclobutanones
1275
References
HO
Br
+
(1) Stevenson, M. H.; Crone, A. V. J.; Hamilton, J. T. G. Nature
1990, 334, 202.
10
14
(2) (a) Stevenson, M. H.; Gray, R. J. Sci. Food Agric. 1989, 48,
261. (b) Lea, J. S.; Dodd, N. J. F. Int. J. Food Sci. Technol.
1988, 23, 625. (c) Boyd, D. R.; Crone, A. V. J.; Hamilton, J.
T. G.; Hand, M. V.; Stevenson, M. H.; Stevenson, P. J. J.
Agric. Food Chem. 1991, 39, 789. (d) Stevenson, M. H.
Trends Food Sci. Technol. 1992, 31, 257. (e) Crone, A. V.
J.; Hand, M. V.; Hamilton, J. T. G.; Sharma, N. D.; Boyd, D.
R.; Stevenson, M. H. J. Sci. Food Agric. 1993, 62, 361.
(f) Hamilton, L.; Stevenson, M. H.; Boyd, D. R.;
Branningen, I. N.; Treacy, A. B.; Hamilton, J. T. G.;
McRoberts, W. C.; Elliott, C. T. J. Chem. Soc., Perkin Trans.
1 1996, 139.
(3) Stevenson, M. H. Food Technol. 1994, 141.
(4) Ndiaye, B.; Horvatovich, P.; Miesch, M.; Hasselmann, C.;
Marchioni, E. J. Chromatogr., A 1999, 858, 109.
(5) Lee, H.-J.; Lee, M.-Y.; Kim, K.-S. J. Food Sci. Nutr. 1999,
4, 270.
2 equiv CuI, 2 equiv NaI, 1.5 equiv K2CO3,
DMF, r.t., 15 h, N2-atmosphere
15 (87%)
HO
HO
20 mol% Pd (Lindlar cat., H2-saturated)
3.5 equiv quinoline, benzene, 0 °C to r.t., 15 h
16 (94%)
1.5 equiv PPh3, 1.5 equiv CBr4,
CH2Cl2, 0 °C to r.t., 8 h
17 (90%)
Br
1) 1.1 equiv of the anion derived from 7
(analogous to the synthesis of 8)
2) excess aq 1 M HCl, r.t., 2 h
(6) Stewart, E. M.; Moore, S.; Graham, W. D.; McRoberts, W.
C.; Hamilton, J. T. G. J. Sci. Food Agr. 2000, 80, 121.
(7) Tewfik, I. H.; Ismael, H. M.; Sumar, S. Int. J. Food Sci. Nutr.
1999, 50, 51.
O
(8) (a) Horvatovich, P.; Miesch, M.; Hasselmann, C.;
Marchioni, E. J. Chromatogr., A 2000, 897, 259.
(b) Horvatovich, P.; Miesch, M.; Hasselmann, C.;
Marchioni, E. J. Chromatogr., A 2000, 968, 251.
(9) Miesch, M.; Ndiaye, B.; Hasselmann, C.; Marchioni, E.
Radiat. Phys. Chem. 1999, 55, 337.
5 (69%)
Scheme 5
(10) (a) Miller, S. A.; Gadwood, R. C. Org. Synth., Coll. Vol. 8;
Wiley and Sons: New York, 1993, 556. (b) Salaün, J.;
Marguerite, J. Org. Synth., Coll. Vol. 7; Wiley and Sons:
New York, 1990, 131. (c) Krief, A.; Ronvaux, A.; Tuch, A.
Bull. Soc. Chim. Belg. 1997, 106, 699. (d) Krief, A.;
Ronvaux, A.; Tuch, A. Tetrahedron 1998, 54, 6903.
(e) Shevchuk, T. A.; Kulinkovich, O. G. Russ. J. Org. Chem.
2000, 36, 491; Chem. Abstr. 2000, 133, 362561.
(11) Miesch, M.; Miesch, L.; Horvatovich, P.; Burnouf, D.;
Delincée, H.; Hartwig, A.; Raul, F.; Werner, D.; Marchioni,
E. Radiat. Phys. Chem. 2002, 65, 233.
(12) Colpaert, J.; Kesteleyn, B.; Boterberg, S.; Stevens, C.; De
Kimpe, N. New Method for the Synthesis of (Z)-2-(5-
Tetradecenyl)cyclobutanone as Marker for Irradiated
Foodstuffs, 4th International Conference on Agro and Food
Physics, May 16-20, 2000, Instanbul (Turkey), Abstract 11,
74.
(t, J = 6.8 Hz, 3 H), 1.25–1.40 (m, 4 H), 1.43–1.79 (m, 6 H), 2.05
(br s, 1 H), 2.15 (tt, J = 7.2, 2.4 Hz, 2 H), 2.21 (tt, J = 6.7, 2.4 Hz, 2
H), 3.12 (quintet, J = 2.4 Hz, 2 H), 3.66 (t, J = 6.5 Hz, 2 H). 13C
NMR (75 MHz, CDCl3): d = 9.75, 14.04, 18.56, 18.74, 22.27, 25.02,
28.51, 31.14, 31.86, 62.43, 74.41, 75.05, 80.07, 80.67. IR (KBr):
3369 cm–1. MS: m/z (%) = 206 (2) [M+], 205 (5), 191 (2), 149 (37),
110 (74), 91 (100), 79 (54). Anal. Calcd for C14H22O: C, 81.50; H,
10.75. Found: C, 81.71; H, 10.94.
(5Z,8Z)-1-Bromo-5,8-tetradecadiene (17). To a solution of 0.25 g
(1.20 mmol) tetradecadienol (16) in 5 mL of dry CH2Cl2 at 0 °C was
added 0.47 g (1.79 mmol, 1.5 equiv) triphenylphosphine and 0.59 g
(1.79 mmol, 1.5 equiv) dried CBr4. The mixture was allowed to
reach r.t. and was stirred for 8 h at this temperature. The solids were
filtered and the filtrate was evaporated in vacuo. Purification of the
obtained bromide 17 was accomplished by flash chromatography
1
(Et2O–hexane 2:8, Rf = 0.75), yield: 90%. H NMR (300 MHz,
CDCl3): d = 0.89 (t, J = 6.7 Hz, 3 H), 1.29–1.41 (m, 6 H), 1.52
(quint, J = 7.3 Hz, 2 H), 1.88 (quint, J = 7.3 Hz, 2 H), 2.02–2.13 (m,
4 H), 2.77 (t, J = 5.6 Hz, 2 H), 3.41 (t, J = 6.7 Hz, 2 H), 5.27–5.44
(m, 4 H). 13C NMR (75 MHz, CDCl3): d = 14.19, 22.68, 25.72,
26.39, 27.32, 28.19, 29.43, 31.63, 32.41, 33.86, 127.73, 128.93,
129.18, 130.49. IR (KBr): 1648, 1457, 670 cm–1. MS: m/z (%) =
272/274 (13) [M+], 188/190 (14), 95 (57), 81 (86), 67 (100). Anal.
Calcd for C14H25Br: C, 61.54; H, 9.22. Found: C, 61.78; H, 9.40.
(13) Logothetis, L. A. J. Am. Chem. Soc. 1965, 87, 749.
(14) Mino, T.; Masuda, S.; Nishio, M.; Yamashita, M. J. Org.
Chem. 1997, 62, 2633.
(15) Bestmann, H. J.; Brosche, T.; Koschatsky, K. H.; Michaelis,
K.; Platz, H.; Vostrowsky, O. Tetrahedron Lett. 1980, 21,
747.
(16) Ivanov, I. V.; Groza, N. V.; Romanov, S. G.; Kuhn, H.;
Myagkova, G. I. Tetrahedron 2000, 56, 553.
(17) Yadav, J. S.; Nanda, S.; Bhaskar Rao, A. Tetrahedron:
Asymmetry 2001, 12, 2129.
Acknowledgment
The authors are indebted to the IWT Flemish Institute for the
Promotion of Scientific-Technological Research in Industry, the
FWO-Flanders, and Ghent University (GOA) for financial support.
Synlett 2004, No. 7, 1273–1275 © Thieme Stuttgart · New York