SYNTHESIS OF [PHENYL-13C6]LACHNANTHOCARPONE
155
TLC plate. Separation using the solvent system Et2O: n-hexane 7:1 resulted in
a red zone (Rf=0.9), which gave 20 mg (79%) of ([ phenyl-13C6]-7. EI-MS: m/z
12
(rel. int.) 307 [M-1]+ (100); HR-MS: found 308.112038 (calculated for
C
14
13C6H14O3: 308.114424); 1H NMR: d 8.71 (H-7, d, J = 8.5 Hz), 7.80 (H-4, d,
J = 7.8 Hz), 7.58 (H-8, dd, J = 8.4, 3.8 Hz), 7.67-7.51 and 7.30-7.13 (H-20– H-
60, m), 7.14 (H-5, d, J = 7.8 Hz), 7.11 (H-3, s), 4.13 ð6-OCH3; sÞ; 13C NMR: d
180.7 (C-1), 158.0 (C-6), 150.1 (C-2), 149.8 (C-9), 144.2 (C-1’, m), 133.2 (C-4),
131.5 (C-8), 129.9-127.0 (C-2’ - C-6’, C-7, C-9a, C-9b, m), 125.8 (C-6a), 123.0
(C-3a), 113.8 (C-3), 106.6 (C-5), 56.6 ð6-OCH3Þ: Analytical data of the
unlabelled compound 7, which was prepared under identical conditions: EI-
MS: m/z (rel. int.) 301 [M-1]+ (100); HR-MS: found 302.095491 (calculated
1
for C20H14O3: 302.094294); H NMR: d 8.71 (H-7, d, J = 8.5 Hz), 7.80 (H-4,
d, J = 7.8 Hz), 7.58 (H-8, d, J = 8.5 Hz), 7.35-7.45 (H-20– H-60, brm), 7.14 (H-
5, d, J = 7.8 Hz), 7.11 (H-3, s), 4.13 ð6-OCH3; sÞ; 13C NMR: d 180.7 (C-1),
158.0 (C-6), 150.1 (C-2), 149.8 (C-9), 144.2 (C-10), 133.2 (C-4), 131.5
(C-8), 129.9 (C-7), 129.2 (C-30/50), 128.9 (C-20/60), 128.2 (C-40), 127.2 (C-9a),
127.0 (C-9b), 125.8 (C-6a), 123.0 (C-3a), 113.8 (C-3), 106.6 (C-5), 56.6
ð6-OCH3Þ:
[phenyl-13C6]2,6-Dihydroxy-9-phenylphenalen-1-one ([phenyl-13C6]lachnantho-
carpone, [phenyl-13C6]-1)
Compound ([ phenyl-13C6]-7 (20 mg, 65 mmol) was refluxed in a N2 atmosphere
with AcOH (4.4 ml) and 48% HBr (0.56 ml) for 10 h. After cooling to room
temperature, the crude product was subjected to liquid–liquid distribution
between H2O (10 ml) and CH2Cl2 (10 ml). Preparative TLC of the organic
phase resulted in [ phenyl-13C6]lachnanthocarpone ([ phenyl-13C6]-1) (16 mg,
84%). TLC: Rf=0.8 (Et2O: n-hexane 7:1); EI-MS: m/z (rel. int.) 293 [M-1]+
12
(100); HR-MS: found 294.100182 (calculated for
1
C
13
13C6H12O3:
294.098773); H NMR: d 8.75 (H-7, d, J = 8.5 Hz), 7.67-7.51 and 7.30-7.13
3
(H-20–H-60, brm), 7.70 (H-4, d, J = 8.0 Hz), 7.59 (H-8, dd, JH-8–C-1 =3.7 Hz,
0
3JH-8–H-7=8.5 Hz), 7.11 (H-3, s), 7.08 (H-5, d, J = 8.0 Hz); 13C NMR: d 180.3
1
(C-1), 157.1 (C-6), 149.6 (C-9, d, JC-9–C-1 = 55 Hz), 149.5 (C-2), 144.1 (C-10,
0
3
0
m), 133.4 (C-4), 130.9 (C-8), 130.3 (C-7, d, JC-7–C-1 =3.7 Hz), 129.8-126.6
(C20–C60, C-9a, C-9b, m), 124.9 (C-6a), 122.0 (C-3a), 113.8 (C-3), 110.5 (C-5).
Analytical data of the unlabelled compound 1, which was prepared under
identical conditions: EI-MS: m/z (rel. int.) 287 [M-1]+ (100); HR-MS: found
1
288.078178 (calculated for C19H12O3: 288.078644); H NMR: d 8.75 (H-7, d,
J = 8.5 Hz), 7.70 (H-4, d, J = 8.0 Hz), 7.59 (H-8, d, 8.5 Hz, ), 7.35-7.45 (H-20–
H-60, m), 7.11 (H-3, s), 7.08 (H-5, d, J = 8.0 Hz); 13C NMR: d 180.3 (C-1),
157.1 (C-6), 149.6 (C-9), 149.5 (C-2), 144.1 (C-10), 133.4 (C-4), 130.9 (C-8),
130.3 (C-7), 129.2 (C-30/50), 128.6 (C-20/60), 127.8 (C-40), 128.6 (C-9a), 126.9
(C-9b), 124.9 (C-6a), 122.0 (C-3a), 113.8 (C-3), 110.5 (C-5).
Copyright # 2004 John Wiley & Sons, Ltd.
J Label Compd Radiopharm 2004; 47: 147–159