P. A. Leber et al. / Tetrahedron 63 (2007) 6331–6338
6337
short-path distillation. Purification of the residue by flash
chromatography (9:1 pentane/ether) gave compound 10
(4.39 g, 24.9 mmol, 60%). IR (film): 3040, 2920, 2865,
1700, 710; MS: 176 (17) (calcd for C12H16O, M+ 176),
1.96 (br s, 4H), 1.71 (m, 4H), 1.50 (m, 2H), 1.32 (m, 2H);
13C NMR (75 MHz, CDCl3): d 130.7/130.4 (]CH), 128.0/
127.7 (]CH), 40.15/40.08 (CH), 26.04/25.95 (CH2),
25.41/25.40 (CH2), 22.28/22.21 (CH2) (compare Ref. 19).
1
104 (10), 97 (43), 80 (100); H NMR (300 MHz, CDCl3):
d 6.26 (t, 1H), 6.12 (t, 1H), 3.09 (br s, 1H), 2.42 (m, 3H),
2.08 (m, 2H), 1.79 (m, 4H), 1.54 (m, 4H); 13C NMR
(125 MHz, CDCl3): d 214.3 (C]O), 134.3 (]CH), 133.0
(]CH), 52.9 (CH), 42.1 (CH), 38.6 (CH2), 35.7 (CH),
31.1 (CH), 29.5 (CH2), 25.8 (CH2), 23.9 (CH2), 20.8 (CH2).
4.2.12. Bicyclohexyl (14). A small sample of 13 was dis-
solved in 85% ethanol and subjected to standard catalytic
hydrogenation to give 14. MS: 166 (9) (calcd for C12H22,
1
M+ 166), 83 (38), 82 (100), 67 (58); H NMR (300 MHz,
CDCl3): d 1.69 (t, 10H), 1.14 (m, 6H), 1.01 (m, 6H); 13C
NMR (75 MHz, CDCl3): d 43.5 (CH), 30.2 (CH2), 26.9 (2
overlapping peaks, CH2). A sample of the flash-vacuum
pyrolysis mixture containing compounds 1–3, and 12
(Fig. 1) from which compound 2 had been removed by pre-
parative GC was dissolved in pentane and subjected to a stan-
dard catalytic hydrogenation. This product mixture, and
coinjection of authentic 14 with the saturated hydrocarbons
from the reduction of the mixture of 1, 3, and 12, gave three
peaks, for 8, 11, and 14.
4.2.8. cis,endo-Tricyclo[6.2.2.02,7]dodec-9-ene (3). A sam-
ple of ketone 10 (1.53 g, 8.69 mmol) was subjected to the
standard LAH reduction to give an alcohol (0.90 g,
5.06 mmol, 58%). IR (film): 3400, 710. A solution of the
crude alcohol in 25 mL of methylene chloride was cooled
in an ice bath; triethylamine (2 mL) and then methane-
sulfonyl chloride (4.6 mL, 6.81 g, 5.94 mmol) were added.
After being stirred at rt overnight, the reaction mixture was
cooled to 0 ꢀC, quenched with ca. 5 mL of cold 1 N HCl, and
then extracted with methylene chloride (3ꢂ25 mL). The or-
ganic extracts were washed with water, 1 N HCl, water, satd
NaHCO3, water, and brine. The organic layer was dried
(MgSO4) and concentrated under reduced pressure to give a
crude mesylate as a colorless oil (0.59 g, 2.3 mmol, 45%). IR
(film): 1610, 1370, 1350, 1170, 730 cmꢃ1. The crude mesy-
late was converted to 3 (0.24 g, 1.5 mmol, 64%) using the
standard LAH reduction method. MS: 162 (2) (calcd for
Acknowledgements
We thank the National Science Foundation for support of
this work through CHE grants 9987838, 0211120, and
0514376 at Syracuse University, and, at Franklin and Mar-
shall College, through CHE-0075097 and CHE-0412907
(MRI, in support of NMR instrumentation). We also ac-
knowledge the Donors of the American Chemical Society
Petroleum Research Fund for partial support of this research
at Franklin and Marshall College.
1
C12H18, M+ 162), 133 (1), 91 (10), 80 (100), 79 (20); H
NMR (300 MHz, CDCl3): d 6.17 (dd, 2H), 2.26 (br s, 2H),
1.69 (m, 2H), 1.50 (m, 6H), 1.29 (m, 6H); 13C NMR
(75 MHz, CDCl3): d 133.2 (]CH), 40.2 (CH), 36.2 (CH),
25.9 (CH2), 25.2 (CH2), 20.3 (CH2).
References and notes
4.2.9. cis-Tricyclo[6.2.2.02,7]dodecane (11). A small sam-
ple of compound 3 was subjected to a standard catalytic hy-
drogenation procedure to give the known saturated tricyclic
compound 11,12,17,18 which was purified by preparative GC.
1H NMR (500 MHz, CDCl3): d 1.55 (m, 2H), 1.43 (m, 2H),
1.25 (m, 8H), 1.10 (m, 8H) (compare Ref. 12); 13C NMR
(125 MHz, CDCl3): d 37.0 (CH), 29.5 (CH), 27.6 (CH2),
23.0 (CH2), 21.0 (CH2), 20.8 (CH2) (compare Ref. 18).
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