J. CHEM. RESEARCH (S), 1998 477
13
Table 1
C NMR data for compounds 1, 4, 10 and 11±14
Compound
a
b
13
Atom
1
4
10
11
12
14
1
2
3
4
5
6
7
8
9
1
2
3
4
5
6
7
8
9
(C)
151.1
116.7
131.2
133.1
129.9
123.8
39.4
151.4
117.2
130.0
133.3
131.6
126.0
39.7
137.7
116.0
147.9
125.0 (C)
131.8
134.0
131.8
125.0
39.5
153.5
115.5
129.7
132.1
129.7
115.5 (CH)
39.2
145.7
115.9
124.6
132.6
118.9
143.4
39.4
137.5
115.7
155.1
117.9 (CH)
129.9
135.2
129.9
117.9
39.4
157.0
110.1
129.4
131.0
122.9
133.2
39.6
137.5
115.7
195.2
38.7
84.6
48.4
148.4
127.1
40.5
156.9
110.3
129.5
131.5
122.7
133.5
39.4
137.6
115.8
189.7
39.9
84.2
49.1
128.3
147.6 (C)
41.2
151.2
117.0
129.8
133.1
131.5
124.8
39.4
137.6
115.8
147.8
126.1 (C)
131.7
133.9
131.7
126.0 (C)
39.4
(CH)
(CH)
(C)
(CH)
(C)
(CH
(CH
(CH
' (C)
' (CH
' (CH)
' (C)
' (CH)
' (CH)
' (CH
' (CH)
' (CH
2
2
2
)
)
)
137.5
115.8
137.8
115.3
2
)
2
)
137.4
116.3
137.4
115.9
132.1
119.6
132.2
119.8
137.2
116.1
2
)
a
b
Multiplicity established from DEPT. Additional peaks for compound 13: 154.4 (C), C-10; 117.9 (CH), C-20; 129.5 (CH), C-30; 135.1
(
C), C-40; 129.5 (CH), C-50; 117.9 (CH), C-60; 39.7 (CH
2
), C-70; 137.4 (CH), C-80; 115.7 (CH
�
3
.ÐA solution of Compound 13.ÐOil. IR (CHCl ) ꢂmax/cm : 3078, 3011, 2914,
2
), C-90.
1
Oxidative Coupling of 10 in the Presence of FeCl
0 in 95% EtOH (2.5 g, 10 ml) was added dropwise to an aqueous
(7.03 g, 625 ml). A constant stream of air was
maintained through the stirred solution for 48 h and the mixture
was then acidi®ed and extracted with Et O. The Et O layer was
in turn extracted with NaOH (2 M); following acidi®cation of the
alkaline extract, a further Et O extract was collected which was
3
1
1697, 1643, 1607, 1502, 1225. HREIMS m/z (intensity %): 398.1882
): 7.05
solution of FeCl
3
(100) (M , C27
H
26
O
3
requires 398.1882), 357 (8). ꢀ
H
(CDCl
3
(2 H, d, J 8.4 Hz, H-30/50), 7.00 (1 H, d, J 8.1, H-3), 6.92 (1 H,
s, H-5), 6.78 (1 H, d, J 8.1 Hz, H-2), 6.73 (2 H, d, J 8.4 Hz,
H-20/60), 5.95 (2 H, m, H-8/80), 5.85 (1 H, m, H-8'), 5.81 (1 H, s,
H-5'), 5.22 (2 H, m, H-9'), 5.04 (4 H, m, H-9/90), 4.76 (1 H, m,
H-3'), 3.31 (4 H, d, J 6.6, H-7/70), 3.17 (1 H, dd, J 17.6, 2.9 Hz,
H-2'), 2.92 (1 H, dd, J 17.6, 5.0 Hz, H-2'), 2.78 (1 H, dd,
J 14.2, 6.9 Hz, H-7'), 2.63 (1 H, dd, J 14.2, 8.0 Hz, H-7').
2
2
2
washed, dried, concentrated under reduced pressure and subjected
to gradient column chromatography to yield unreacted 10 (1.45 g),
1
(323 mg), 4 (68 mg) and 11 (29 mg).
Oxidative Coupling of 10 in the Presence of K
�
1
Compound 14.ÐPink solid. mp 168 8C. IR (CHCl ) ꢂmax/cm :
3
3
Fe(CN)
6
ÐA
K
3
Fe(CN)
6
solution (1.85 g, 6.4 ml, 0.88 M) was added dropwise
CO
0.8 g, 18.7 ml) at 0 8C. The reaction mixture was stirred for 3 h,
3528, 3275 (br), 3082, 3011, 2914, 1636, 1497, 1229. HREIMS m/z
(intensity %): 530.2457 (100) (M , C36H
over 30 min to a stirred solution of 10 (0.5 g) in aqueous Na
(
then acidi®ed and extracted with Et
subjected to gradient column chromatography to yield unreacted 10
2
3
O
34 4
requires 530.2457). ꢀ
H
(CDCl
3
): 7.20 (2 H, dd, J 2.2 Hz, H-3'), 7.17 (2 H, d, J 2.2 Hz,
2
O, worked up as before and
H-5'), 7.12 (2 H, d, J 2.2 Hz, H-5), 7.09 (2 H, dd, J 8.2, 2.2 Hz,
H-3), 6.89 (2 H, d, J 8.2 Hz, H-2), 5.95 (4 H, m, H-8/8'), 5.07
(8 H, m, H-9/9'), 3.41 (2 H, d, J 6.7 Hz, H-7'), 3.36 (4 H, d,
J 6.7 Hz, H-7).
(
(
107 mg), 1 (59 mg, 8%), 4 (132 mg, 11%), 11 (35 mg, 5%), 12
94 mg, 12%), 13 (54 mg, 5%) and 14 (55 mg, 4%).
�
1
Magnolol (1).ÐOil. IR (CHCl ) ꢂmax/cm : 3549, 3267 (br), 3082,
3
3
011, 2907, 1639, 1497, 1215. HREIMS m/z (intensity %): 266.1305
requires 266.1307), 248 (5), 247 (6), 237 (9),
We thank the CRCG for funding this research.
(
100) (M , C18
H
18
O
2
2
25 (15). ꢀ
H
(CDCl
3
): 7.12 (2 H, dd, J 8.2, 2.1 Hz, H-3), 7.08 (2 H,
Received, 26th February 1998; Accepted, 11th May 1998
Paper E/8/01620H
d, J 2.1 Hz, H-5), 6.94 (2 H, d, J 8.2 Hz, H-2), 5.95 (2 H, m,
H-8), 5.05 (4 H, m, H-9), 3.35 (4 H, d, J 6.7 Hz, H-7).
�
1
Dunnianol (4).ÐSolid. Mp 133.5±134.5 8C. IR (CHCl ) ꢂmax/cm :
3
References
3
545, 3315 (br), 3085, 3011, 2926, 1640, 1506, 1215. HREIMS m/z
(
(
(
intensity %): 398.1882 (75) (M , C27
13), 287 (100), 266 (29). ꢀ
H
26
O
3
requires 398.1882); 316
): 7.14 (2 H, s, H-3'/5'), 7.12
2 H, d, J 2.1 Hz, H-5), 7.10 (2 H, dd, J 8.1, 2.1 Hz, H-3),
.92 (2 H, d, J 8.1 Hz, H-2), 5.96 (3 H, m, H-8/8'), 5.10 (6 H, m,
H-9/9'), 3.36 (6 H, d, J 6.1 Hz, H-7/7').
-Allylphenol (10).ÐOil. ꢀ (CDCl ): 7.14 (1 H, br, s, 1-OH),
1 L.-K. Sy, R. M. K. Saunders and G. D. Brown, Phytochemistry,
1997, 44, 1099.
2 I. Kouno, T. Morisaki, Y. Hara and C.-S. Yang, Chem. Pharm.
Bull., 1991, 39, 2606.
3 I. Kouno, A. Hashimoto, N. Kawano and C.-S. Yang, Chem.
Pharm. Bull., 1989, 37, 1291.
H 3
(CDCl
6
4
H
3
7
5
.02 (2 H, d, J 8.3 Hz, H-3/5), 6.77 (2 H, d, J 8.3 Hz, H-2/6),
4 I. Kouno, C. Iwamoto, Y. Kameda, T. Tanaka and C.-S. Yang,
Chem. Pharm. Bull., 1994, 42, 112.
.95 (1 H, m, H-8), 5.05 (2 H, m, H-9), 3.31 (2 H, d, J 6.7 Hz,
H-7).
5 L.-K. Sy and G. D. Brown, Phytochemistry, 1996, 43, 1417 (see
also erratum in Phytochemistry, 1997, 45, 211).
6 I. Kouno, Y. Yanagida, S. Shimono, M. Shintomi, Y. Ito and
C.-S. Yang, Phytochemistry, 1993, 32, 1573.
7 O. R. Gottlieb, Phytochemistry, 1972, 11, 1537.
8 R. S. Ward, Nat. Prod. Rep., 1995, 12, 183 and preceding reviews.
9 R. S. Ward, Chem. Soc. Rev., 1982, 11, 75.
10 T. I. Ho, C. C. Tsau, D. L. Chen and F. C. Chen, Hua Hsueh,
1985, 43, 1.
�
1
Isomagnolol (11).ÐOil IR (CHCl
922, 1636, 1506, 1229. HREIMS m/z (intensity %); 266.1306 (100)
3
) ꢂmax/cm : 3566, 3011, 2978,
2
(
M , C18
18 2 H
H O requires 266.1307), 175 (8), 134 (12), 133 (12). ꢀ
(
CDCl
3
): 7.15 (2 H, d, J 8.4 Hz, H-3'/5'), 6.96 (1 H, d, J 8.2 Hz,
H-2), 6.93 (2 H, d, J 8.4 Hz, H 2'/6'), 6.84 (1 H, dd, J 8.2,
1
5
.8 Hz, H-3), 6.70 (1 H, d, J 1.8 Hz, H-5), 5.95 (2 H, m, H-8/8'),
.49 (1 H, s, 1-OH), 5.05 (4 H, m, H-9/9'), 3.36 (2 H, d, J 6.6 Hz,
H-7'), 3.24 (2 H, d, J 6.6 Hz, H-7).
�
1
Compound 12.ÐOil. IR (CHCl
639, 1487, 1250. HREIMS m/z (intensity %): 266.1305 (91) (M ,
3
) ꢂmax/cm : 3013, 2905, 1686,
11 M. R. Agharahimi and N. A. LeBel, J. Org. Chem., 1995, 60,
1856.
1
C
18
H
18
O
2
requires 266.1307), 239 (13), 225 (100), 197 (16), 184 (14),
): 7.02 (1 H, d, J 1.7 Hz, H-5), 6.99 (1 H, dd, J 8.2,
12 M. Iguchi, A. Nishiyama, Y. Terada and S. Yamamura, Chem.
Lett., 1978, 451.
13 M. Iguchi, A. Nishiyama, Y. Terada and S. Yamamura,
Tetrahedron Lett., 1977, 4511.
14 J. B. Press, Synth. Commun., 1977, 9, 407.
15 H. Erdtman and J. Runeberg, Acta Chem. Scand., 1957, 11,
1060.
16 C. G. Haynes, A. H. Turner and W. A. Waters, J. Chem. Soc.,
1956, 2823.
H 3
ꢀ (CDCl
1
.7 Hz, H-3), 6.72 (1 H, d, J 8.2 Hz, H-2), 6.49 (1 H, dd,
J 10.2, 1.8 Hz, H-5'), 5.99 (1 H, d, J 10.2 Hz, H-6'), 5.94 (1 H,
m, H-8), 5.78 (1 H, m, H-8'), 5.19 (2 H, m, H-9'), 5.07 (2 H, m,
H-9), 4.80 (1 H, m, H-3'), 3.33 (2 H, d, J 6.7 Hz, H-7), 3.00 (1 H,
dd, J 17.6, 2.8 Hz, H-2'), 2.79 (1 H, dd, J 14.2, 6.7 Hz, H-7'),
2
8
.74 (1 H, dd, J 17.6, 4.2 Hz, H-2'), 2.66 (1 H, dd, J 14.2,
.1 Hz, H-7').