SHORT PAPER
A New Convenient Synthesis of Alkoxyanthracenes from Alkoxy-9,10-anthraquinones
2465
Table 1 Substituents in Compounds 1 and 3 (see Scheme 2)
tion of 1,8-dichloro-9,10-anthraquinone with tetraethyl-
ene glycol in anhydrous THF in the presence of sodium
hydride, could be easily reduced by zinc in refluxing ace-
tic acid to afford the 1,8-oxybis(ethyleneoxyethylene-
oxy)anthracene (5) in good yield (Scheme 3). In the H
NMR spectrum, the compound 5 showed two singlets at
1, 3
b
c
R1
R2
R3
H
R4
R5
H
R6
H
OMe
H
H
H
1
OMe
H
H
H
H
H
9.39 and 8.30 ppm for H-9 and H-10 , respectively.
d
e
OMe
OMe
H
OMe
H
H
H
H
H
OMe
H
H
H
O
f
OMe
OMe
H
H
OMe
H
H
Zn/HOAc/reflux 7h
g
OMe
OMe
OCH2CO2Et
H
OMe
OMe
H
OMe
OMe
H
O
O
O
O
O
70%
h
i
OMe
H
H
O
O
O
O
O
O
H
H
4
5
Scheme 3
Table 2 Alkoxyanthracenes 3 and Compound 5 Prepared
Sub-
strate
Prod-
uct
Time
(h
Yield
(%)
mp
Lit. mp (°C) or
1H NMR (CDCl3)c
, J (Hz
(°C)a
Molecular Formulab
1a
3a
16
75
195–196
1975
9.24 (s, 1 H), 8.32 (s, 1 H), 7.57 (d, J = 8.50, 2 H), 7.38 (dd,
J = 8.50, 7.47, 2 H), 6.74 (d, J = 7.47, 2 H), 4.09 (s, 6 H,
OCH3)
1b
3b
12
75
70–71
70–7210
8.86 (s, 1 H), 8.39 (s, 1 H), 8.05–8.08 (m, 1 H), 7.99–8.02 (m,
1 H), 7.60 (d, J = 8.56, 1 H), 7.45–7.50 (m, 2 H), 7.39 (dd,
J = 8.56, 7.37, 1 H), 6.76 (d, J = 7.37, 1 H), 4.11 (s, 3 H,
OCH3)
1c
3c
12
71
183–184
183.1–183.611
8.36 (s, 1 H), 8.29 (s, 1 H), 7.94–7.99 (m, 2 H), 7.90 (d,
J = 9.11, 1 H), 7.41–7.46 (m, 2 H), 7.21 (s, 1 H), 7.18 (d,
J = 9.11, 1 H), 3.98 (s, 3 H, OCH3)
1d
1e
1f
3d
3e
3f
15
12
24
62
70
60
134–136
227–228
261–262
134–1364a
2288
8.79 (s, 2 H), 8.03–8.07 (m, 2 H), 7.47–7.50 (m, 2 H), 6.62 (s,
2 H), 4.04 (s, 6 H, OCH3)
8.80 (s, 2 H), 7.65 (d, J = 8.54, 2 H), 7.37 (dd, J = 8.54, 7.39,
2 H), 6.77 (d, J = 7.39, 2 H), 4.09 (s, 6 H, OCH3)
260–2625
8.23 (s, 2 H), 7.56 (d, J = 8.96, 2 H), 7.20 (s, 2 H), 7.17 (d,
J = 8.96, 2 H), 4.09 (s, 6 H, OCH3)
1g
1h
3g
3h
24
24
50
52
297–299
128–130
298–30012
9.12 (s, 2 H), 6.65 (s, 4 H), 4.05 (s, 12 H, OCH3)
C18H18O4 (298.12)
9.00 (s, 1 H), 8.74 (s, 1 H), 7.83 (d, J = 9.15, 1 H), 7.38 (d,
J = 9.15, 1 H), 6.60 (ABq, 2 H), 4.11(s, 3 H, OCH3), 4.06 (s,
6 H, OCH3), 4.04 (s, 3 H, OCH3)d
1i
4
3i
5
6
7
65
70
oil
C18H16O3 (280.11)
C22H24O5 (368.37)
8.99 (s, 1 H), 8.40 (s, 1 H), 8.10–8.13 (m, 1 H), 8.00–8.03 (m,
1 H), 7.67 (d, J = 8.57, 1 H), 7.48–7.54 (m, 2 H), 7.35 (dd,
J = 8.57, 7.38, 1 H), 6.66 (d, J = 7.38, 1 H), 4.90 (s, 2 H), 4.37
(q, J = 7.13, 2 H), 1.35 (t, J = 7.13, 3 H)d
157–158
9.39 (s, 1 H), 8.30 (s, 1 H), 7.56 (d, J = 8.56, 2 H), 7.35 (dd,
J = 8.56, 7.34, 2 H), 6.69 (d, J = 7.34, 2 H), 4.36 (t, J = 3.79,
4 H), 4.16 (t, J = 3.79, 4 H) 3.88–3.95 (m, 8 H)d
a Uncorrected.
b Satisfactory microanalyses obtained: C 0.17, H 0.11.
c Recorded on Bruker AM-300 spectrometer.
d 13C NMR (CDCl3)c: 3h: = 55.5, 57.1, 61.1, 100.2, 100.9, 114.0, 116.7, 120.8, 124.3, 125.1, 125.6, 127.5, 128.5, 142.4, 147.0, 149.3, 149.4;
3i: = 14.1, 61.4, 65.6, 102.7, 121.3, 121.6, 124.7, 125.2, 125.6, 125.7, 127.8, 128.8, 131.3, 132.0, 132.5, 153.6, 168.8; 5: = 68.6, 69.2,
70.2, 71.4, 102.2, 116.4, 120.4, 124.5, 125.0, 125.6, 132.9, 155.1.
Synthesis 2003, No. 16, 2464–2466 © Thieme Stuttgart · New York