2.39 (2H, t, J 2.1), 3.31 (3H, s, OMe), 4.7 (1H, t, J 2.1) and 5.01
(1H, t, J 2.1); δC (75 MHz) 15.239 (q), 22.95 (t), 24.18 (t), 29.79
(t), 29.94 (t), 36.23 (t), 41.34 (t), 41.4 (t), 51.82 (q), 55.19 (s),
56.42 (s), 57.18 (s), 80.03 (s), 107.3 (t), 156.58 (s) and 218.8 (s);
m/z 246 (Mϩ, 6%), 218 (27), 134 (100) and 83 (72) (Found: Mϩ,
246.3468. C16H22O2 requires M, 246.3478).
7-Methyl-9-methylene-3-oxotricyclo[4.3.3.01,6]dodecane-7-
carbonitrile 10
Method A. Beckmann fragmentation with p-TsCl. To a stirred
solution of the oxime 9 (0.4 g, 1.5 mmol) in dry pyridine (7 ml)
was added a solution of p-TsCl (0.35 g, 1.8 mmol) in dry pyrid-
ine (2 ml) at 0 ЊC over a period of 10 min. The reaction mixture
was stirred at room temperature for 24 h and poured into dil.
HCl. Usual work-up followed by chromatography on silica gel
[ethyl acetate–‘hexane’ (1:10)] furnished the nitrile 10 (0.29 g,
83%) as a colourless oil, νmax/cmϪ1 2220, 1710, 1650 and 900;
δH (300 MHz) 1.50 (3H, s, Me), 1.54–2.55 (10H, m), 2.52 (1H,
d, J 15.3, Ha-8), 2.6 and 2.68 (2H, ABq, J 16.2), 2.89 (1H, d,
J 15.3, Hb-8) and 4.95 and 5.07 (2H, br s, olefinic); δC (75 MHz)
20.6 (q), 24.6 (t), 30.4 (t), 34.5 (t), 34.7 (t), 43.0 (t), 46.3 (s), 46.8
(t), 49.0 (t), 55.2 (s), 56.4 (s), 108.2 (t), 124.7 (s), 155.0 (s) and
211.6 (s); m/z 229 (Mϩ, 52%), 213 (21), 202 (88), 162 (68), 91
(100), 55 (72) (Found: Mϩ, 229.3217. C15H19NO requires M,
229.3211).
7-Methoxytricyclo[5.2.2.01,5]undec-5-en-8-one oxime 17
A magnetically stirred solution of the ketone 6 (0.5 g, 2.6
mmol), hydroxylamine hydrochloride (0.36 g, 5.2 mmol) and
sodium carbonate (0.83 g, 7.8 mmol) in a mixture of ethanol
(6 ml) and water (12 ml) was refluxed for 4 h. The reaction mix-
ture was cooled and the product was extracted with ether. The
organic layer was subjected to the usual work-up followed
by chromatography on silica gel [ethyl acetate–‘hexane’ (1:10)]
which furnished the oxime 17 (0.49 g, 90%), which was crystal-
lised from ethyl acetate–‘hexane’, mp 108–109 ЊC; νmax/cmϪ1
3300, 1650 and 930; δH (90 MHz) 1.21–1.86 (8H, m), 2.12 (1H,
dd, J1 17.4, Jw 3.3, H-9 endo), 2.18–2.39 (2H, m, allylic CH2),
2.46 (1H, d, J 17.4, H-9 endo), 3.53 (3H, s, OMe) and 5.98
(1H, br s, olefinic) (Found: C, 69.8; H, 8.3; N, 6.5. C12H17NO2
requires C, 69.5; H, 8.3; N, 6.8%).
Method B. Beckmann fragmentation with trifluoromethane-
sulfonic anhydride. To a magnetically stirred solution of the
oxime 9 (0.13 g, 0.5 mmol) and dry pyridine (0.047 ml, 0.6
mmol) in dry dichloromethane (2 ml) at 0 ЊC was added tri-
fluoromethanesulfonic anhydride (0.09 ml, 0.55 mmol) slowly
dropwise. After being stirred for 3 h at the same temperature,
aqueous NaHCO3 solution was added and the product was
extracted with ether. The organic layer was washed with water,
brine and dried over anhydrous Na2SO4. Removal of the solvent
followed by chromatography on silica gel furnished the keto
nitrile 10 (91 mg, 83%), identical with the sample obtained as
above.
6-(Cyanomethyl)bicyclo[4.3.0]non-1-en-3-one 18
Method A. Beckmann fragmentation with p-TsCl. To a solu-
tion of the oxime 17 (0.4 g, 1.9 mmol) in dry pyridine (5 ml) was
added a solution of p-TsCl (0.44 g, 2.3 mmol) in dry pyridine (3
ml) at 0 ЊC over a period of 10 min. The reaction mixture was
stirred at room temperature for 36 h and poured into dil. HCl.
Usual work-up followed by chromatography on silica gel [ethyl
acetate–‘hexane’ (1:10)] afforded the keto nitrile 18 (0.3 g,
88%), which was recrystallised from ‘hexane’, mp 68 ЊC; νmax
/
cmϪ1 2225 and 1660; δH (300 MHz) 1.55–1.66 (2H, m), 1.84–
2.04 (4H, m), 2.19–2.26 (1H, m), 2.39–2.78 (5H, m) and 5.9 (1H,
t, J 2.4); δC (22.5 MHz) 20.3 (t), 22.4 (t), 29.9 (t), 32.1 (t), 32.3
(t), 37.4 (t), 43.8 (s), 116.9 (s), 122.7 (d), 172.2 (s) and 197.2 (s)
(Found: C, 75.4; H, 7.5; N, 8.0. C11H13NO requires C, 75.4; H,
7.6; N, 8.0%).
7-Methoxy-9-exo-methyl-9-(prop-2-ynyl)tricyclo[5.2.2.01,5]-
undec-5-en-8-one oxime 19
A stirred solution of the ketone 14 (0.5 g, 2 mmol) and hydroxyl-
amine hydrochloride (1.13 g, 16 mmol) in pyridine (10 ml) was
refluxed for 48 h. After cooling to room temperature, the reac-
tion mixture was poured into dil. HCl and extracted with ether.
The extract was subjected to the usual work-up, followed by
chromatography on silica gel and elution with ethyl acetate–
‘hexane’ (1:10) to afford the oxime 19 as a white solid, which was
crystallised from ethyl acetate–‘hexane’ (0.4 g, 75%), mp 132–
133 ЊC; νmax/cmϪ1 3300, 1650 and 900; δH (300 MHz) 1.5 (3H, s,
Me), 1.2–1.77 (8H, m), 1.95 (1H, t, J 2.7), 2.28 (1H, dd, J 17.7
and 2.7), 2.35–2.52 (2H, m, allylic CH2), 2.99 (1H, dd, J 17.7
and 2.7), 3.51 (3H, s, OMe) and 5.90 (1H, br s, olefinic) (Found:
C, 74.2; H, 8.1; N, 5.3. C16H21NO2 requires C, 74.1; H, 8.2;
N, 5.4%).
Method B. Beckmann fragmentation with trifluoromethane-
sulfonic anhydride. To a magnetically stirred solution of the
oxime 17 (0.12 g, 0.58 mmol) and dry pyridine (0.005 ml, 0.7
mmol) in dry methylene dichloride (1 ml) at 0 ЊC was added
trifluoromethanesulfonic anhydride (0.1 ml, 0.64 mmol) slowly
dropwise. After being stirred at the same temperature for 3 h the
mixture was treated with aq. NaHCO3 and the product was
extracted with ether. The extract was submitted to the usual
work-up, followed by chromatography to furnish the keto
nitrile 18 (83 mg, 81%), which was recrystallised from ‘hexane’,
mp 68–69 ЊC, identical with the sample obtained in the above
experiment.
2-Methyl-2-(4-oxobicyclo[4.3.0]non-5-en-1-yl)pent-4-ynonitrile
20
8-Methoxy-10-methyl-12-methylenetetracyclo[6.4.1.01,5.05,10]-
Method A. Beckmann fragmentation with p-TsCl. To a stirred
solution of the oxime 19 (0.4 g, 1.5 mmol) in dry pyridine
(5 ml) was added a solution of p-TsCl (0.36 g, 1.8 mmol) in dry
pyridine (3 ml) dropwise over a period of 10 min at 0 ЊC. After
the addition was over the reaction mixture was stirred at room
temperature for 24 h and poured into dil. HCl. Usual work-up
followed by chromatography on silica gel and elution with ethyl
acetate–‘hexane’ (1:10) afforded the keto nitrile 20 (0.29 g, 82%)
as a white solid, mp 128–129 ЊC; νmax/cmϪ1 3250, 2220 and 1660;
δH (300 MHz) 1.56 (3H, s, Me), 1.59–1.93 (4H, m), 2.25 (1H,
t, J 3, acetylenic CH), 2.32–2.97 (8H, m), 6.13 (1H, d, J 2.4,
olefinic); m/z Mϩ (227, 16%), 212 (6), 199 (27), 184 (25), 160
(41), 135 (89), 107 (100), 93 (48) (Found: Mϩ, 227.3043.
C15H17NO requires M, 227.3052).
tridecan-9-one oxime 9
A solution of the ketone 8 (0.5 g, 2 mmol) and hydroxylamine
hydrochloride (1.13 g, 16 mmol) in pyridine (7 ml) was refluxed
for 48 h. The solution was poured in to dil. HCl and the product
was extracted with ether. The organic layer was subjected to the
usual work-up, followed by chromatography [ethyl acetate–
‘hexane’ (1:10)] to afford the tetracyclic oxime 9 (0.4 g, 75%),
which was recrystallised from ‘hexane’–ethyl acetate, mp 176–
177 ЊC; νmax/cmϪ1 3250, 1650 and 890; δH (300 MHz) 1.42 (3H,
s, Me), 1.44–2.17 (10H, m), 1.89 (2H, d, J 1.5, CH2), 2.33 (2H,
td, J 16.5 and 2.1), 3.0 (1H, t, J 16.5, allylic CH), 3.3 (3H, s,
OMe), 4.7 (1H, t, J 2.1) and 4.96 (1H, t, J 2); δC (75 MHz) 15.6
(q), 22.9 (t), 24.8 (t), 29.4 (t), 29.6 (t), 36.8 (t), 39.0 (t), 45.6 (t),
49.2 (s), 51.1 (q), 54.7 (s), 56.8 (s), 75.6 (s), 106.8 (t), 158.9 (s)
and 164.4 (s) (Found: C, 73.3; H, 8.9; N, 5.3. C16H23NO2
requires C, 73.5, H, 8.9; N, 5.4%).
Method B. Beckmann fragmentation with trifluoromethane-
sulfonic anhydride. To a magnetically stirred solution of the
J. Chem. Soc., Perkin Trans. 1, 2000, 4512–4519
4517