978
Russ.Chem.Bull., Int.Ed., Vol. 54, No. 4, April, 2005
Spivak et al.
temperature. The catalyst was filtered off, and the filtrate was
concentrated. The residue was chromatographed on a column
with SiO (20 g). A fraction of nonpolar substances (R 0.7) was
(MeC(4´) and MeC(8´)); 20.50 (MeCO); 20.59 and 21.00
(C(4)); 22.58 and 22.68 (2 MeC(12´)); 23.65 (MeC(2)); 24.38,
24.75 (C(2´), C(6´), C(10´)); 27.90 (C(12´)); 30.95 (C(3));
32.61, 32.70 (C(4´), C(8´)); 37.23, 37.33, 37.50 (C(3´), C(5´),
C(7´), C(9´)); 39.31 (C(11´)); 39.99 and 40.06 (C(1´));
75.65 (C(2)); 113.95 (C(5)); 120.21, 121.90, 124.46, 126.0
(C(7)—C(10)); 124.78, 125.72, 126.33 (C(4а), C(6а), C(10а));
136.79 (C(10b)); 146.63 (C(6)); 169.54 (MeCO).
(2RS)ꢀ6ꢀHydroxyꢀ2,5ꢀdimethylꢀ2ꢀ(4RS,8RS,12ꢀtrimethylꢀ
tridecanꢀ1ꢀyl)ꢀ3,4ꢀdihydroꢀ2Hꢀnaphtho[1,2ꢀb]pyrans (7). A soꢀ
lution of diastereomeric mixture 6 (0.28 g, 0.57 mmol) and
lithium alumohydride (0.02 g, 0.53 mmol) in anhydrous diethyl
ether (22.7 mL) was refluxed for 1 h (Ar) with stirring. The
reaction mixture was cooled to 0 °C, and wet ether (2 mL) and
then 3 M hydrochloric acid (0.5 mL) were added. The ethereal
layer was separated, washed with water to the neutral pH, dried
2
f
isolated by elution with nꢀhexane, and the evaporation of the
next fraction (R 0.4), which was eluted with a hexane—Et O
f
2
(
10 : 1) mixture, gave a 1 : 1 mixture of erythroꢀ and
threoꢀdiastereomers 4 (0.21 g, 48%) as a viscous oily substance,
1
8
[
α]D –1.0 (c 2.0, CHCl ). Found (%): C, 78.71; H, 8.91.
3
–
1
C H O . Calculated (%): C, 78.49; H, 8.96. IR, ν/cm : 1760
2
5
34
3
(
C=O); 1210, 1080 and 1060 (C—O). UV (CHCl ), λmax/nm (ε):
3
1
2
2
1
45 (76709), 309 (4883), 330 (4257). H NMR, δ: 0.92 (m, 6 H,
MeC(5´)); 1.04 (d, 1.5 H, MeC(1´), J = 6.7 Hz); 1.15 (d,
.5 H, MeC(1´), J = 6.8 Hz); 1.32 (s, 3 H MeC(2)); 1.20—2.10
(
(
m, 10 H, 2 H(3), H(1´)—H(5´)); 2.25 (s, 3 H, MeC(5)); 2.54
s, 3 H, MeCO); 2.75 (t, 2 H, H(4), J = 6.7 Hz); 7.48 (m, 2 H,
H(8), H(9)); 7.70 and 8.28 (both d, 2 H, H(7), H(10), J =
1
3
8
.4 Hz). C NMR, δ: 12.56 (MeC(5)); 13.57 and 14.24
with MgSO , and concentrated in vacuo. Compound 7 was obꢀ
4
(
(
(
MeC(1´)); 20.30 and 20.38 (C(4)); 20.56 (MeCO); 22.43, 22.64
MeC(2), 2 MeC(5´)); 25.76 and 25.81 (C(3´)); 27.75, 27.84
C(5´), C(1´)); 30.77, 31.48 (C(2´), C(3)); 39.13 (C(4´)); 78.27,
tained in 77% yield (0.2 g) as a viscous dark yellow oil. IR,
–
1
1
ν/cm : 1080, 1060 (C—O); 3400 (OH). The UV and H NMR
4
13
spectra are identical to those presented earlier.
C NMR, δ:
7
1
8.33 (C(2)); 114.24 and 114.28 (C(5)); 120.19, 121.86, 124.47,
26.02 (C(7)—C(10)); 124.79, 125.72, 126.33 (C(4а), C(6а),
15.27 (MeC(5)); 19.78, 19.86 (MeC(4´), MeC(8´)); 21.01 and
21.18 (C(4)); 22.75 and 22.85 (2 MeC(12´)); 23.60 (MeC(2));
24.56, 24.93 (C(2´), C(6´), C(10´)); 28.07 (C(12´)); 31.52
(C(3)); 32.78, 32.87 (C(4´), C(8´)); 37.39, 37.49, 37.69 (C(3´),
C(5´), C(7´), C(9´)); 39.47 (C(11´)); 39.91 and 39.96 (C(1´));
75.12 (C(2)); 114.48 (C(5)); 117.50, 124.44, 124.57 (C(4а),
C(6а), C(10а)); 120.63, 121.66, 124.44, 125.08 (C(7)—C(10));
141.08 (C(10b)); 142.88 (C(6)).
(2RS)ꢀ6ꢀAcetoxyꢀ2,5ꢀdimethylꢀ2ꢀ(4ꢀmethylpentꢀ3ꢀenꢀ1ꢀyl)ꢀ
3,4ꢀdihydroꢀ2Hꢀnaphtho[1,2ꢀb]pyran (10) and 9ꢀacetoxyꢀ
1,1,4а,10ꢀtetramethylꢀ1,2,3,4,4аRS,11аꢀhexahydroꢀ1Hꢀbenꢀ
zo[h]xanthene (11). A. Linalool 8 (0.22 g, 1.4 mmol) was slowly
added under argon to a boiling suspension of compound 1 (0.60 g,
2.8 mmol) and powdered Zeocarꢀ10 catalyst (1.0 g) in anhydrous
toluene (9 mL). The reaction mixture was refluxed for 5 h and
cooled to room temperature. The catalyst was filtered off, and
the filtrate was concentrated. The residue was chromatographed
C(10а)); 136.67 (C(10b)); 146.48 (C(6)); 169.68 (MeCO).
B. A similar reaction of compound 1 (0.5 g, 2.3 mmol) with
reflux for 5 h, under the conditions of experiment A, gave (after
column chromatography) a 2 : 1 mixture of compounds 3 and 4
(
0.3 g, 68%). The spectroscopic characteristics of compound 3
1
were found from the spectra of a mixture of 3 and 4. H NMR
for 3, δ: 0.92 (m, 6 H, 2 MeC(8´)); 1.04, 1.10 (both d, 1.5 H each,
MeC(4´), J = 6.7 Hz); 1.30—2.10 (m, 8 H, H(4´)—H(8´)); 1.75
(
s, 3 H, MeC(3´)); 2.29 (s, 3 H, MeC(2)); 2.55 (s, 3 H, MeCO));
3
6
.40 (d, 2 H, H(1´), J = 6.1 Hz); 5.24 (t, 1 H, H(2´), J =
.1 Hz); 6.08 (br.s, 1 H, OH); 7.45 (m, 2 H, H(6), H(7)); 7.70
13
and 8.10 (both d, 2 H, H(5), H(8), J = 7.7 Hz). C NMR, δ:
2.51 (MeC(2)); 13.31 (MeC(3´)); 19.86 (MeC(4´)); 20.51
1
(
(
(
MeCO); 22.52 (2 MeC(8´)); 25.84 (C(6´)); 26.25 (C(5´)); 27.81
C(8´)); 35.03 (C(1´)); 38.95 (C(7´)); 42.74 (C(4´)); 120.17
C(2´)); 120.35, 121.85, 124.44, 125.87 (C(5)—C(8)); 124.80,
on a column with SiO (20 g). A fraction of nonpolar substances
2
1
1
25.68, 126.07 (C(2), C(3), C(4а), C(8а)); 137.66 (C(3´));
42.84 (C(4)); 147.62 (C(1)); 169.80 (MeCO).
(R 0.7) was isolated by elution with nꢀhexane, and the next
f
fraction (R 0.4) was eluted with an nꢀhexane—Et O (10 : 1)
f
2
(
2RS)ꢀ6ꢀAcetoxyꢀ2,5ꢀdimethylꢀ2ꢀ(4RS,8RS,12ꢀtrimethylꢀ
decanꢀ1ꢀyl)ꢀ3,4ꢀdihydroꢀ2Hꢀnaphtho[1,2ꢀb]pyrans (6). Isophytol
(0.4 g, 1.35 mmol) was slowly added under argon to a boiling
mixture. Evaporation of this fraction gave a viscous oil (0.45 g),
which crystallized on standing. After treatment with nꢀhexane,
product 11 was filtered off. The yield was 0.31 g (63%), m.p.
191—193 °C. Found (%): C, 78.16; H, 7.81. C H O . Calcuꢀ
5
suspension of compound 1 (0.56 g, 2.6 mmol) and powdered
Zeocarꢀ10 catalyst (1.1 g) in anhydrous toluene (9 mL). The
reaction mixture was refluxed for 4 h and cooled to room temꢀ
perature. The catalyst was filtered off, and the filtrate was conꢀ
centrated. The residue was chromatographed on a column with
SiO (20 g). The fraction of nonpolar substances (R 0.7) was
2
3
28
3
lated (%): C, 78.38; H, 8.01. IR, ν/cm– : 1760 (C=O); 1210,
1
1080, 1060 (C—O). UV (CHCl ), λmax/nm (ε): 245 (34650), 308
3
1
(6410), 330 (5396). H NMR, δ: 1.00, 1.10 (both s, 6 H,
2 MeC(1)); 1.30 (s, 3 H, MeC(4а)); 1.40—1.90 (m, 6 H,
H(2)—H(4)); 2.15 (m, 1 H, H(11а)); 2.28 (s, 3 H, MeC(10));
2.50 (m, 1 H, H(11), 3 H, MeCO); 2.80 (dd, 1 H, H(11), J =
16.1 Hz, J = 5.2 Hz); 7.48 (m, 2 H, H(6), H(7)); 7.70 and 8.28
2
f
eluted with nꢀhexane, and the evaporation of the next fraction
R 0.4), which was eluted with an nꢀhexane—Et O (10 : 1)
mixture, gave diastereomeric mixture 6 (0.56 g, 84%).
Found (%): C, 80.42; H, 10.03. C H O . Calculated (%):
C, 80.11; H, 10.19. IR, ν/cm–1: 1760 (C=O); 1210, 1080, and
060 (C—O). UV (EtOH), λmax/nm (ε): 244 (40493), 305 (5365),
28 (3925). H NMR, δ: 0.95 (m, 12 H, MeC(4´), MeC(8´),
MeC(12´)); 1.00—1.80 (m, 23 H, H(1´)—H(12´), H(3)); 1.35
(
f
2
13
(both d, 2 H, H(8), H(5), J = 8.0 Hz). C NMR, δ: 12.60
(MeC(10)); 20.55 (2 MeC(1), MeCO); 21.69 (C(1)); 32.03
(MeC(4а)); 33.33 (C(3), C(11)); 39.71 (C(2)); 41.50 (C(4));
47.92 (C(11а)); 75.41 (C(4а)); 114.00 (C(10а)); 120.04, 120.15,
121.97, 124.43, 124.62, 125.91, 125.99 (C(5)—C(8), C(4C),
C(8а), C(10)); 136.86 (C(4b)); 146.01 (C(9)); 169.66 (MeCO).
B. Compound 8 (0.71 g, 4.6 mmol) was slowly added under
argon to a boiling suspension of compound 1 (1.0 g, 4.6 mmol)
and CSA catalyst (0.11 g, 0.47 mmol) in anhydrous nꢀoctane
(9 mL). The reaction mixture was refluxed for 3 h, then cooled
3
3
50
3
1
3
2
1
and 1.40 (both s, 3 H, MeC(2)); 2.28 (s, 3 H, MeC(5)); 2.51 (s,
H, MeCO); 2.76 (t, 2 H, H(4), J = 6.4 Hz); 7.50 (m, 2 H,
H(8), H(9)); 7.70 and 8.30 (both d, 2 H, H(7), H(10), J =
3
1
3
8
.1 Hz). C NMR, δ: 12.56 (MeC(5)); 19.63 and 19.69