1
916
T. Nguyen Van et al.
LETTER
(
0.22 g, 67%). Spectroscopic data of 2,3-diallyl-5,7-
anthraquinone (12d, 0.06 g, 88%). Spectroscopic data of 1,4-
dimethoxy-1,4-naphthoquinone (6a, 62%). Yellow crystals,
dihydro-5,7-dimethoxy-9,10-anthraquinone (12a, 91%).
Yellow crystals, mp 191 °C. H NMR (270 MHz, CDCl ):
1
mp 111 °C. Flash chromatography R = 0.08 (hexane–
f
3
1
EtOAc 4:1). H NMR (270 MHz, CDCl ): d = 3.35–3.40 (4
d = 3.19 (4 H, s), 3.94 and 3.96 (6 H, 2 × s), 5.84 (2 H, s),
3
6.71 (1 H, d, J = 2.2 Hz), 7.25 (1 H, d, J = 2.2 Hz). 1 C NMR
3
H, m), 3.93 and 3.96 (6 H, 2 × s), 5.03–5.23 (4 H, m), 5.79–
5
.93 (2 H, m), 6.71 (1 H, d, J = 2.3 Hz), 7.26 (1 H, d, J = 2.3
(67.8 MHz, CDCl ): d = 24.15, 24.58, 55.89, 56.37, 102.97,
3
1
3
Hz). C NMR (67.8 MHz, CDCl ): d = 30.60, 31.09, 55.90,
6.42, 102.93, 104.06, 116.62, 116.71, 133.99, 134.28,
36.06, 142.14, 147.04, 161.70, 164.40, 182.67, 184.90. IR
= 1651 cm . MS (70 eV): m/z (%) = 299 (100)
M + 1]. All other new compounds were fully characterized
103.92, 114.43, 122.55, 123.09, 135.96, 138.78, 143.63,
3
5
1
161.71, 164.37, 182.75 and 184.60. IR (KBr): n
= 1652
C=O
–
1
+
cm . MS (70 eV): m/z (%) = 271 (100) [M + 1], 269 (48).
–
1
1
(
[
KBr): n
All other new compounds were fully characterized by H
C=O
+
13
NMR, C NMR, IR and MS.
1
13
by H NMR, C NMR, IR and MS.
16) Ashnagar, A.; Malcolm Bruce, J.; Lloyd-Williams, P. J.
(22) As a representative example, the synthesis of 9,10-
anthraquinone 13d is described. A solution of 1,4-dihydro-
9,10-anthraquinone (12d, 50.70 mg, 0.238 mmol) and
palladium on active carbon (10%) (25.3 mg, 0.024 mmol,
0.10 equiv) in dry toluene (10 mL) was refluxed for 12 h.
(
(
Chem. Soc., Perkin Trans. 1 1988, 559.
17) (a) Araki, S.; Katsumura, N.; Butsugan, Y. J. Organomet.
Chem. 1991, 415, 7. (b) Hagiwara, E.; Hatanaka, Y.; Gohda,
K.-I.; Hiyama, T. Tetrahedron Lett. 1995, 36, 2773.
18) Nguyen Van, T.; Kesteleyn, B.; De Kimpe, N. Tetrahedron
®
The cooled reaction mixture was filtered over Celite and
(
washed with CH Cl (3 × 10 mL). Removal of the solvent in
2
2
2001, 57, 4213.
vacuo afforded the pure 9,10-anthraquinone 13d (46.50 mg,
94%). The anthraquinones 13 were recrystallized from
EtOH. 1,3-Dimethoxy-9,10-anthraquinone (13a, 91%). The
spectral data correspond well with those reported in the
(
(
19) Naruta, Y. J. Am. Chem. Soc. 1980, 102, 3774.
20) Motoyoshiya, J.; Kameda, T.; Asari, M.; Miayamoto, M.;
Narita, S.; Aoyama, H.; Hayashi, S. J. Chem. Soc., Perkin
Trans. 2 1997, 1845.
2
3
23
literature. Yellow crystals, mp 159 °C (Lit. mp 158–
1
(
21) As a representative example, the synthesis of 1,4-dihydro-
160 °C). H NMR (270 MHz, CDCl ): d = 3.99 and 4.02 (6
3
9,10-anthraquinone 12d is described. To a solution of 2,3-
H, 2 × s), 6.80 (1 H, d, J = 2.3 Hz), 7.47 (1 H, d, J = 2.3 Hz),
1
3
diallyl-1,4-naphthoquinone (6d, 0.08 g, 0.330 mmol) in
7.67–7.81 (2 H, m), 8.20–8.29 (2 H, m). C NMR (67.8
CH Cl (35 mL), Grubbs’ catalyst was added [benzylidene-
bis(tricyclohexylphosphine)dichlororuthenium, 0.02 g,
MHz, CDCl ): d = 56.44, 57.02, 103.81, 105.25, 116.60,
2
2
3
126.97, 127.69, 132.85, 133.30, 134.79, 135.63, 138.01,
0
1
.023 mmol, 0.07 equiv] at r.t. After heating under reflux for
2 h, the cooled reaction mixture was filtered over silica gel
163.09, 165.23, 181.76, 183.99. IR (KBr): n
= 1673
C=O
–
1
+
cm . MS (70 eV): m/z (%) = 269 (100) [M + 1].
and washed with CH Cl (3 × 50 mL). Removal of the
(23) Khanapure, S. P.; Reddy, R. T.; Biehl, E. R. J. Org. Chem.
1987, 52, 5685.
2
2
solvent in vacuo afforded pure 1,4-dihydro-9,10-
Synlett 2004, No. 11, 1913–1916 © Thieme Stuttgart · New York