9
24
M. C. Davis and A. J. Sathrum
14 mL of glacial HOAc (0.26 mol, 1 equiv) in 400 mL of H O. After 30 min,
all the material had dissolved and the emulsion cleared. The organic layer was
2
separated and washed with 400 mL of H O, followed by 400 mL of brine. The
2
organic phase was dried over 20 g of anhydrous MgSO for 1 h, filtered, then
4
treated with 1 g of decolorizing charcoal for 1 h. The mixture was filtered and
rotary evaporated (408C, 10 Torr) to leave a yellow-orange semisolid. The
crude was reslurried with a mixture of 200 mL of Et O and 100 mL of
2
EtOAc for 2 h. The mixture was filtered on a 350-mL coarse-porosity glass-
fritted funnel. The bright yellow powder was placed under vacuum to
remove residual solvent (56.4 g, 69%). The material was sufficiently pure
1
(
.95% by H NMR) and was recrystallized from EtOAc to give orange
chunky crystals. Mp 124–1258C. d : 7.37 (d, J ¼ 9.2 Hz, 2H), 6.93
H
(
d, J ¼ 16.5 Hz, 1H), 6.72 (d, J ¼ 8.7 Hz, 2H), 6.7 (d, J ¼ 16.5 Hz, 1H),
ab
ab
5
.98 (s, 1H), 3.82 (t, J ¼ 6.0 Hz, 2H), 3.57–2.4 (m, 4H), 2.5 (bs, OH), 2.45
(
s, 2H), 2.28 (s, 2H), 1.19 (t, J ¼ 7.3 Hz, 3H), 1.09 (s, 6H); d : 200.58,
C
1
5
56.49, 149.14, 135.82, 129.15, 125.03, 124.71, 124.02, 112.20, 60.21,
2.46, 51.52, 45.66, 39.25, 33.44, 28.67, 12.18. Anal. calcd. for
C H NO : C, 76.64; H, 8.68; N, 4.47. Found: C, 76.64; H, 8.73; N, 4.41.
2
0
27
2
(1S-cis) 4-[4-[N-Ethyl-N-(2-hydroxyethyl)amino]styryl]-6,6-
dimethyl-bicyclo[3.1.1]hept-3-ene-2-one, 4
In similar fashion, 18.6 g of verbenone (0.124 mol, 1.3 equiv), 6.9 g of
powdered KOH (0.124 mol, 1.3 equiv), and 18.36 g of 1 (0.095 mol, 1
equiv) were reacted for 5 h at 608C. A similar workup procedure gave 36 g
of a crude red-orange oil, which, after EtOAc reslurry, gave 13.6 g of 95%
pure title compound (44%). The material was recrystallized from EtOAc to
give orange crystals. Mp 124–1258C. d : 7.38 (d, J ¼ 8.9 Hz, 2H), 6.87
H
(
(
d,
J
¼ 16.0 Hz, 1H), 6.79–6.66 (m, 3H), 5.82 (s, 1H), 3.82
ab
t, J ¼ 5.8 Hz, 2H), 3.58–3.39 (m, 4H), 3.12 (t, J ¼ 5.8 Hz, 1H), 2.88 (dt,
J ¼ 9.3 and 5.8 Hz, 1H), 2.69 (td, J ¼ 5.8 and 1.8 Hz, 1H), 2.29 (bs, OH),
2
1
5
.09 (d, J ¼ 9.3 Hz, 1H), 1.19 (t, J ¼ 7.1 Hz, 3H), 1.00 (s, 3H); d : 204.78,
C
65.81, 149.18, 135.81, 129.31, 124.12, 122.70, 120.31, 112.27, 60.28,
8.29, 52.91, 52.48, 45.71, 43.99, 40.19, 26.97, 22.33, 12.19. Anal. calcd.
for C H NO : C, 77.5; H, 8.36; N, 4.3. Found: C, 77.23; H, 8.27; N, 4.25.
2
1
27
2
E 3-[4-[N,N-Bis-(2-hydroxyethyl)amino]styryl]-5,5-
dimethylcyclohex-2-enone, 5
In similar fashion, 3.17 g of isophorone (0.023 mol), 1.29 g of KOH (0.023 mol,
1 equiv) and 4.79 g 2 (0.023 mol, 1 equiv) were reacted for 5 h at 608C. A
similar workup procedure gave 5.7 g of a crude red-orange oil, which, after
EtOAc reslurry, gave 2.8 g of 95% pure title compound (37%), which was