692
K. Mori / Tetrahedron: Asymmetry 16 (2005) 685–692
COCH2), 3.26 (1H, m, CH2CHCH3), 5.42 (1H, d, J 8.1,
NH), 5.83 (1H, m, HNCHCH3), 7.07–8.06 (11H, m,
ArH); dC (CDCl3): 20.3, 21.0, 21.8, 36.7, 44.4, 46.0,
122.5, 123.5, 125.1, 125.8, 126.5, 126.7, 128.3, 128.7,
129.2, 131.0, 133.8, 135.9, 138.1, 142.7, 170.5. Anal.
Calcd for C23H22NO (331.5): C, 83.34; H, 7.60; N,
4.23. Found C, 83.25; H, 7.62; N, 4.19.
Acknowledgements
I would thank Bartelt (US Department of Agriculture)
and Tamogami (T. Hasegawa Co., Ltd) for discussions
and their help in GC analysis. Thanks are due to Tashiro
and Masuda (both at RIKEN) for HPLC analysis. I am
grateful to Hagiwara, the president, Chuman and Muto
(all at Fuji Flavor Co., Ltd) for their support of this work.
4.14. (R)-1,2,5,8-Tetramethyl-1,2,3,4,5-penta-
hydrobenzo[a][7]annulen-3-one 23
References
To a stirred and cooled solution of (R)-6 (1.0 g,
4.6 mmol) in CS2 (15 mL) was added powdered AlCl3
(1.1 g, 83 mmol) portionwise over 1 h at ꢀ40 to
ꢀ20 ꢁC under Ar. The mixture was then stirred and
heated under reflux (46 ꢁC = bp of CS2) for 1 h. After
cooling, the mixture was poured into ice and dil HCl,
and extracted with hexane. The extract was washed with
water and brine, dried over MgSO4, and concentrated in
vacuo. The residue was chromatographed over SiO2
(30 g) in hexane. Elution with hexane/EtOAc (20:1) first
gave the recovered (R)-6 (0.4 g, 40%), and then the
´
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22
D
½aꢁ ¼ ꢀ52:7 (c 0.85, CHCl3). mmax (film): 1710 (s,
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CO), 1305 (m), 815 (m); dH (CDCl3): 1.41 (3H, s,
CH3): 1.44 (3H, d, J 6.9, CHCH3), 1.49 (3H, s, CH3),
2.31 (3H, s, ArCH3), 2.32 (1H, dd, J 11, 13, CHH),
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CHH), 3.26 (1H, d, J 12, CHH), 3.61 (1H, m, CHCH3),
7.01 (1H, dd, J 1, 8, ArH), 7.14 (1H, d, J 8, ArH), 7.21
(1H, d, J 1, ArH); dC (CDCl3): 20.6, 21.0, 32.3, 33.0,
33.5, 38.7, 52.6, 53.9, 126.3, 127.2, 128.7, 136.0, 138.9,
145.3, 211.0. Anal. Calcd for C15H20O (213.3): C,
83.28; H, 9.32. Found C, 83.13, H, 9.39.
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hydrobenzo[a][7]annulene (ar-himachalene) 1
A solution of KOH (2.0 g) in water (2 mL) and
N2H4ꢂH2O (2 mL) were added to a solution of (R)-23,
(390 mg, 1.9 mmol) in diethylene glycol (20 mL). The
mixture was stirred and heated under reflux for 1 h,
and then heated at 200–210 ꢁC for 3 h with removal of
the volatile materials. After cooling, the mixture was di-
luted with water and extracted with hexane. The extract
was washed with water and brine, dried over MgSO4,
and concentrated in vacuo. The residue was chromato-
graphed over SiO2 (5 g) in hexane. Elution with hexane
gave 154 mg (42%) of (R)-1 as a colorless oil,
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23
23
n2D6 ¼ 1:5068; ½aꢁ ¼ ꢀ2:4 (c 1.19, CHCl3); ½aꢁ ¼ þ3:8
D
D
(c 1.18, hexane). mmax (film): 1610 (w, Ar), 810 (s); dH
(CDCl3): 1.33 (3H, s, CH3), 1.34 (3H, d, J 6.9, CHCH3),
1.42 (3H, s, CH3), 1.45–1.60 (1H, m, CHH), 1.60–1.69
(1H, m, CHH), 1.70–1.86 (4H, m, CH2), 2.31 (3H, s,
ArCH3), 3.25 (1H, m, CHCH3), 6.99 (1H, dd, J 1, 8,
ArH), 7.12 (1H, d, J 8, ArH), 7.19 (1H, d, J 1.5, ArH);
dC (CDCl3): 21.0, 21.2, 24.0, 29.7, 33.9, 34.4, 36.5, 39.5,
41.1, 125.4, 126.5, 127.5, 134.9, 141.2, 147.7. Anal. Calcd
for C15H22 (202.3): C, 89.04; H, 10.96. Found C, 88.65;
H, 11.07. The enantiomeric purity of (R)-1 was deter-
mined as 97.7% ee by Dr. Bartelt employing chiral GC
technique. GC: Column, CDX-B at 120 ꢁC; tR
40.63 min [(S)-1, 1.1%], 41.18 min [(R)-1, 98.8%].