4826
M. Bella et al. / Tetrahedron 60 (2004) 4821–4827
trimethylchlorosilane (0.25 mL, 2.0 mmol) was added
dropwise under stirring. After 1 h, 10 (102 mg, 0.5 mmol),
in 2 mL of dry Et2O, was added under stirring. After 1 h, the
reaction mixture was allowed to warm up to room
temperature. The usual work up as previously described
furnished 88 mg of 13 (yield 80%) as an inseparable 3:1
trans/cis diastereoisomeric mixture.
References and notes
1. (a) Bauer, K.; Garbe, D.; Surburg, H. Common Fragrance and
Flavor Materials; Wiley-VCH: Weinheim, 1997. (b) Frater,
G.; Bajgrowicz, J. A.; Kraft, P. Tetrahedron 1998, 54,
7633–7703. (c) Kraft, P.; Bajgrowicz, J. A.; Denis, C.; Frater,
G. Angew. Chem., Int. Ed. Engl. 2000, 39, 2980–3010.
2. (a) Gautier, A.; Vial, C.; Morel, C.; Lander, M.; Naf, F. Helv.
Chim. Acta 1987, 70, 2039–2044. (b) Vial, C.; Thommen, W.;
Naf, F. Helv. Chim. Acta 1989, 72, 1390–1399. (c) Ohloff, G.
In Fragrance Chemistry; Theimer, E. T., Ed.; Academic: New
York, 1982; p 535. (d) Ohloff, G. Experientia 1986, 42,
271–279. (e) Ohloff, G.; Naf, F.; Decorzant, R.; Thommen,
W.; Sundt, E. Helv. Chim. Acta 1973, 56, 1414–1448.
3. (a) Hall, J. B.; Sanders, J. M. US Patent 3,929,677, 1975.
(b) Erman, M. B.; Williams, M.; Whelan, P.; Cardenas, C.;
Antipin, M. Perfum. Flavor. 2001, 16, 18–21. (c) Erman,
M. B.; Williams, M. J.; Cardenas, C. G. US Patent 6,423,874,
2002.
In both methods, the formation of 12 as viscous oil and as a
side product derived from 1,2-addition was detected, with a
variable yield (method a: 24%; method b: 15%). IR nmax
(CHCl3)/cm21: 3370, 1660, 1358, 1110. 1H NMR (d,
CDCl3): 5.93 (1H, s), 2.25–1.95 (6H, m), 1.70–1.40 (4H,
m), 1.42 (6H, s), 1.08 (6H, s). 13C NMR (d, CDCl3): 138.9,
134.2, 128.4 (Cquat), 120.2, 77.0 (Cquat), 39.4; 32.2; 31.3;
29.7; 28.1; 25.2; 22.1; 19.7. HRMS calcd for C15H24O
[MþNH4]þ 238.1827, found 238.1830.
4.1.6. 1-[4-Methyl-4-(4-methyl-3-pentenyl)-1-cyclo-
hexenyl]ethan-1-one, 15. Compound 11 (102 mg,
0.5 mmol), under the same reaction conditions and purifi-
cation to prepare 13 (method a), gave 15 as oil (72 mg, yield
65%). IR nmax (CHCl3)/cm21: 1685, 1660, 1358, 1210,
1111. 1H NMR (d, CDCl3): 6.82 (1H, m); 5.08 (1H, m); 2.28
(3H, s); 2.23 (1H, m); 2.04 (2H, m); 1.95 (2H, m); 1.67 (3H,
s); 1.59 (3H, s); 1.42 (2H, m); 1.24 (2H, m); 0.88 (3H, s).
13C NMR (d, CDCl3): 193.0 (CvO); 139.5, 126.4 (Cquat);
124.8; 122.1; 49.0; 43.1; 42.1; 37.3; 32.8; 27.5; 25.8; 21.9;
17.8. HRMS calcd for C15H24O [MþNH4]þ 238.1827,
found 238.1825.
4. Nussbaumer, C.; Frater, G.; Kraft, P. Helv. Chim. Acta 1999,
82, 1016–1024.
5. (a) See Ref. 1: Frater, G.; Bajgrowicz, J. A.; Kraft, P.
Tetrahedron 1998, 54, 7633–7703, and literature therein,
especially Refs. [2–6,8]. For a compilation on perfume
classics, see Edwards, M. Perfume Legends, French Feminine
Fragrances, Crescent House Publishing, La Quinta, CA
92253, 1996. (b) Bajgrowicz, J. A.; Bringhen, A.; Frater, G.;
Muller, U. Eur. Pat. Appl. 743297, 1996; U.S. Patent
5,707,961, 1998. (c) Erman, M. B.; Hoffmann, H. M.;
Cardenas, C. G. Eur. Pat. Appl. 985651, 2000; U.S. Patent
6,160,182, 2000.
4.1.7. (1,2)-1-[(1R p,2S p)-1,2,3,4,5,6,7,8-Octahydro-
1,2,8,8-tetramethylnaphthalen-2-yl]ethan-1-one,
Georgywood, 3. A trans/cis mixture of 13 (160 mg,
0.72 mmol) was dissolved in dry THF (10 mL) under
argon at 0 8C, then NaH (70 mg, 2.9 mmol) and CH3I
(750 mg, 5.28 mmol) were added. The reaction mixture was
allowed to warm up to room temperature, then to reflux for
48 h. The reaction mixture, diluted with Et2O (50 mL), was
treated with MeOH (0.5 mL), then washed, water (5 mL)
until neutrality, brine (3 mL) and dried over anhydrous
Na2SO4. The organic layer was concentrated in vacuum and
the product was purified by flash chromatography (hexane/
ethyl acetate 20/1) to give the fragrant oil, Georgywood, 3,
as viscous oil and as only one diastereoisomer (101 mg,
yield 60%). IR nmax (CHCl3)/cm21: 2928, 2832, 1702,
1459, 1376, 1357, 1239, 1219, 1195, 1126, 1090, 1065,
1028, 964. 1H NMR (d, CDCl3): 2.36 (1H, q); 2.15 (3H, s);
2.1–1.7 (6H, m); 1.55–1.4 (4H, m); 1.06 (3H, s); 1.02 (3H,
s); 0.99 (3H, s); 0.86 (3H, d, J¼6.6 Hz). 13C NMR (d,
CDCl3): 214.4 (CvO); 136.9, 125.9 (CvC); 50.7 (C2 q);
40.1; 35.4 (C1); 34.0 (C8 q); 30.8; 29.4, 28.4 (CH3); 27.6;
24.8 (CH3); 22.5; 21.0, 19.7 (CH3); 19.1. HRMS calcd for
C16H26O [MþNH4]þ 252.1984, found 252.1988.
6. Fringuelli, F.; Taticchi, A. Dienes in the Diels–Alder
Reaction; Wiley: New York, 1990; Chapter 1, pp 23–25,
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Acknowledgements
We thank COFIN 2002 (Roma) and the University ‘La
Sapienza’ of Rome for financial support. We are grateful to
Professor G. Frater (Givaudon Schweiz AG) for a generous
gift of a pure sample of Georgywood.
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2000, 56, 2799–2804.