Absolute Conguration And Tautomeric Structure Of Xylindein Page 3
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1
2
3
4239
H
HH
H
spectrometer. The chemical shifts were reported as
16.8 Hz, H-1
, 1
), 3.42 (2H,
=2.8, 16.8 Hz, H-1
,
HH
H
HH
values in ppm relative to TMS as an internal standard,
1
), 4.08 (6H, , 3-, 9- Me), 4.56 (2H,
, H-2
, 2
), 6.48
H
13
unless otherwise stated. Low and high resolution mass
(2H, , H-5, 11);
C NMR (CDCl
, TMS) 13.9 (C-5
,
3
HH
H
HH
H
HH
H
HH
spectra were obtained on a JEOL GCmate (EI) and a
5
), 18.2 (C-4
, 4
), 28.0 (C-1
, 1
), 36.8 (C-3
, 3
), 63.6
H
HH
Hewlett Packard HP5989A (TSI) mass spectrometers.
(3-, 9- Me), 77.3 (C-2
, 2
), 111.0 (C-5, 11), 118.0 (*),
Elemental analysis was performed on a YANACO,
120.0 (*), 121.0 (*), 124.8 (*), 133.2 (*), 142.4 (*), 153.6
CHN-Corder-MT-5.
(*), 158.0 (C-3, 9), 159.9 (2-, 8-C=O), 180.7 (C-4, 10) [*:
C-1, 7 or C-2, 8 or C-3a, 9a or C-5a, 11a or C-6a, 12a or
1
C-9b, 12b or C-12c, 12d we could not assign these car-
bons because the sample could not withstand the long
time measurement (irradiation in the strong magnetic
®eld), such as INADEQUATE (measured in CD
OD±
3
CDCl
+
Xylindein (1) (45 mg) was extracted from 20 g of both
(1:5)).]; EI±HR±MS
598.1850 [M+2H]
,
3
the fruiting bodies of
species (
calcd for C
H
O
, 598.1838.
34
30
10
, and
) and the infected
wood with re¯uxing CHCl
(500 ml) according to the
3
3
procedure of Edwards and Kale (1965). The crude 1 was
recrystallized from hot 80% aqueous PhOH to give
magenta plates (28 mg). 1
4PhOH: m.p. >200
C (lit;
>300
C [Edwards and Kale, 1965)]; UV, l
5%
A suspension of xylindein dimethyl ether (2: 300 mg)
max
2,2,2-tri¯uoroethanolÀCHCl
nm (log 4): 658 (4.60),
and 10% Pd-C (30 mg) in THF (80 ml) was stirred for
3
611 (4.45), 488 (3.55), 428 (4.09), 405 (4.21), 384 (4.19),
0.5 h under an atmospheric pressure of H
. The mixture
2
nujol
348 (4.59), 256 (4.65); IR #
cm
À1
: 1699, 1625, 1592,
was rapidly ®ltered through Celite and the ®ltrate was
max
1
1300, 1241, 1190, 1080, 1064, 980, 885, 842, 805;
H
evaporated in vacuo, giving an orange amorphous solid
NMR (300 MHz, CF
CO
D, TMS) 1.10 (6H,
(3, 301 mg). A small portion of this was subjected to
3
2
H
HH
H
HH
=6.3 Hz, H-5
, 5
), 1.72 (4H, , H-4
, 4
), 1.98 (2H, ,
silica gel chromatography in order to obtain an analy-
H
HH
H
HH
H-3
, 3
), 2.09 (2H,
, H-3
, 3
), 3.33 (2H,
=11.7,
tical sample.
H
HH
H
HH
27
17.3 Hz, H-1
, 1
), 3.91 (2H,
=17.3 Hz, H-1
, 1
), 4.91
[]
À789.5 (CHCl
, 0.04); UV, l
CHCl
nm (log
D
3
max
3
H
HH
KBr
(2H,
, H-2
, 2
), 7.32 (2H, , H-5, 11), 6.92 (8H,
,
4): 442 (4.62), 415 (4.63), 322 (4.52), 259 (4.57); IR #
max
À1
PhOH), 7.03 (4H, , PhOH), 7.27 (8H, , PhOH); TSI±
cm
: 3320, 2959, 2938, 2877, 1708, 1619, 1608, 1582,
+
MS,
/ 569 [M+H]
; Elemental analysis, found: C
1499, 1417, 1381, 1362, 1238, 1150, 1104, 1063, 1019,
70.63, H 4.87%, calcd for C
H
O
: C 71.18, H 5.12%.
962, 940, 838, 762;
1
H NMR (CDCl
, TMS) 1.02 (6H,
56
48
14
3
H
HH
H
HH
1 (free from PhOH):
1
H NMR (300 MHz, CF
CO
D,
=7.0 Hz, H-5
, 5
), 1.60 (4H, , H-4
, 4
), 1.73 (2H, ,
3
2
H
HH
H
H
HH
H
HH
TMS) 1.11 (6H,
=6.9 Hz, H-5
, 5
), 1.71 (4H, , H-4
,
H-3
, 3
), 1.85 (2H,
, H-3
, 3
), 2.42 (2H,
=11.2,
HH
H
HH
H
HH
H
HH
H
4
), 1.98 (2H, , H-3
, 3
), 2.09 (2H, , H-3
, 3
), 3.33 (2H,
16.8 Hz, H-1
, 1
), 2.90 (2H,
=2.5, 16.8 Hz, H-1
,
H
HH
HH
H
HH
=11.7, 17.5 Hz, H-1
, 1
), 3.90 (2H,
=17.5 Hz,
1
), 4.06 (6H, , 3-, 9- Me), 4.39 (2H,
, H-2
, 2
), 6.12
H
HH
H
HH
H-1
, 1
), 4.92 (2H,
, H-2
, 2
), 7.32 (2H, , H-5, 11).
(2H, , H-5, 11), 9.33 (2H, , 4-, 10-OH);
13
C NMR
H
HH
H
HH
(CDCl
, TMS) 13.9 (C-5
, 5
), 18.2 (C-4
, 4
), 27.2 (C-
3
H
HH
H
HH
H
HH
2
1
, 1
), 36.9 (C-3
, 3
), 64.3 (3-, 9- Me), 77.2 (C-2
, 2
),
101.4 (C-5, 11), 102.6 (*), 112.3 (*), 113.5 (*), 118.5 (*),
124.3 (*), 143.6 (*), 146.8 (*), 155.2 (C-4, 10), 155.8 (C-
3, 9), 162.3 (2-, 8-C=O) (*: C-1, 7 or C-2, 8 or C-3a, 9a
Xylindein (1, 500 mg) suspended in CHCl
(360 ml)
or C-5a, 11a or C-6a, 12a or C-9b, 12b or C-12c, 12d);
3
+
was methylated with CH
N
(1 M in Et
O, 20 ml)
EI±HR±MS
598.1841 [M]
, calcd for C
H
O
,
2
2
2
34
30
10
according to the procedure of Edwards and Kale (1965)
598.1838.
and the resulting crude methyl ether was subjected to
silica gel chromatography (eluted with 20% acetone±
4
CHCl
) to give 2 (300 mg) as a magenta amorphous
3
solid.
UV, l
CHCl
nm (log 4): 570 (4.58), 525 (4.42), 488
max
3
(4.04), 455 (3.67), 405 (3.96), 382 (4.04), 339 (4.49), 259
KBr
(4.50); IR #
cm
À1
: 3460, 2940, 2870, 1738, 1719,
To a solution of the above crude dihydroxylindein
max
1639, 1580, 1450, 1327, 1200, 1103, 1072, 1040, 978,
dimethyl ether (3, 301 mg) and 4-bromobenzyl bromide
1
942, 850;
H NMR (CDCl
, TMS) 1.04 (6H,
=
(377 mg, 1.5 equiv.) in DMF (10 ml, degassed and ®lled
3
H
HH
H
HH
7.6 Hz, H-5
, 5
), 1.65 (4H, , H-4
, 4
), 1.83 (2H, , H-
with Ar) was added a suspension of NaH (27 mg, 1.1
H
HH
H
HH
3
, 3
), 1.94 (2H,
, H-3
, 3
), 2.91 (2H,
, =11.5,
equiv.) in DMF (13 ml, degassed and ®lled with Ar).
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