Synthesis of 9-anthryl ethers from trans-9,10-dihydro-9,10- dimethoxyanthracene by acid-catalyzed transetherification

Article abstract of DOI:10.1055/s-0028-1088073

During a study of electrophilic aromatic addition reactions (Ad _EAr) to anthracene, anthryl ethers at the C9-position of anthracene were obtained as the major products when trans-9,10-dihydro-9,10- dimethoxyanthracene was reacted (10 minutes at

Full text of DOI:10.1055/s-0028-1088073

PAPER
1703
Synthesis of 9-Anthryl Ethers from trans-9,10-Dihydro-9,10-dimethoxy-
anthracene by Acid-Catalyzed Transetherification
S
ynthesis of 9-Ant
e
hryl
E
thers
u
byAcid-Ca
t
n
alyzed
T
ransetherif
S
ication am Jang,a Hee Young Shin,a Dae Yoon Chi*b
a
Department of Chemistry, Inha University, 253 Yonghyundong Namgu, Inchon 402-751, Korea
Department of Chemistry, Sogang University, 1 Shinsudong Mapogu, Seoul 121-742, Korea
Fax +82(2)7010967; E-mail: dychi@sogang.ac.kr
b
Received 9 December 2008; revised 30 January 2009
ing 2-methoxyanthracene with various alcohols and thiols
in the presence of trifluoromethanesulfonic acid.10,11
Abstract: During a study of electrophilic aromatic addition reac-
tions (AdEAr) to anthracene, anthryl ethers at the C9-position of an-
thracene were obtained as the major products when trans-9,10-
dihydro-9,10-dimethoxyanthracene was reacted (10 minutes at
75 °C) with various alcohols. 9-Anthryl ethers with primary, sec-
ondary, cyclic alcohols, and polyethylene glycol (PEG) were isolat-
ed in 47–73% yields under optimized conditions. It is hoped that the
devised method offers a new synthetic route for the preparation of
anthryl ethers via the acid-catalyzed transetherification of trans-
9,10-dihydro-9,10-dimethoxyanthracene with various alcohols.
Here, we describe an efficient method for the synthesis of
9-alkoxyanthracene
from
trans-9,10-dihydro-9,10-
dimethoxyanthracene (1) via acid-catalyzed transetherifi-
cation using primary, secondary, or cyclic alcohols, poly-
ethylene glycol (PEG), or natural alcohols like
dihydrocholesterol or epiandrosterone.
OMe
Key words: transetherification, anthryl ethers, trans-9,10-dihydro-
O
9,10-dimethoxyanthracene
propan-1-ol
H2SO4, 75 °C
10 min
OMe
Anthracene and its derivatives have been utilized for a va-
riety of optical electronic devices, such as light emitting
diodes,1 field effect transistors,2 and fluorescent
chemosensors.3 In particular, anthryl ethers have attracted
considerable interest due to their unique chemical reactiv-
ities and photochromic properties for the construction of
photoresponsive supramolecular systems4 and for the syn-
thesis of triptycenes and triptycene quinones.5 Several
methods have been devised to synthesize 9-anthryl ethers,
such as, the etherification of 9-anthrone with alcohols un-
der acidic conditions,6 alkylation via aromatization by
phase transfer catalysis,7 and direct alkoxylation using
cerium(IV) tetrakistrifluoroacetate (CTFA).8 However,
these methods are limited, because the starting 9-anthrol
is as the minor tautomeric form of the 9-anthrol and
9-anthrone tautomerization. Thus, under the William
ether synthetic conditions, 10-alkylated 9-anthrone could
be obtained as major product.
1
2c (65%)
Scheme 1 Preparation of 9-propoxyanthracene from trans-9,10-di-
hydro-9,10-dimethoxyanthracene (1) in the presence of H2SO4 in pro-
pan-1-ol
Recently, we described electrophilic aromatic addition
(AdEAr) reactions of fused aromatic compounds, such as,
naphthalenes and quinolines.12 During our study of
anthracene AdEAr reactions,13 we found trans-9,10-dihy-
dro-9,10-dimethoxyanthracene (1) was converted into 9-
alkoxylated anthracene by transetherification at the C9-
position, and that the addition of a catalytic amount of sul-
furic acid accelerated this reaction and improved the se-
lectivity for 9-anthryl ethers synthesis. In addition, we
also reported the selective re-aromatization to 9-methoxy-
anthracene (2a) from 1 by an elimination reaction in a
basic methanolic solution at room temperature, and 9-pro-
poxyanthracene (2c) (65% yield) from 1 in the presence of
propan-1-ol and sulfuric acid when reacted for 10 minutes
at 75 °C in addition to 9-methoxyanthracene (2a) and an-
thracene (3). We believe that this phenomenon offers a
valuable means of producing anthryl ethers on the B-ring
of anthracene.13
Even though the B-rings are much more reactive towards
reagents, 9-alkoxyanthracenes are produced with difficul-
ty. In addition, previously described methods require high
reaction temperatures and long reaction times, and sto-
ichiometric amounts or large excesses of reagents. Fur-
thermore, it has been reported that the hydrolysis of 9-
anthryl ethers produces 9-anthrone and alcohols in the
presence of strong acid.9 The above limitations encour-
aged us to develop a new methodology for the synthesis
of 9-alkoxyanthracenes. Recently, various anthryl ethers
were prepared with common functional groups, by react-
Table 1 summarizes the results of reactions between
trans-9,10-dihydro-9,10-dimethoxyanthracene (1) and a
number of alcohols under various conditions. To deter-
mine optimal conditions, we carried out the reaction using
different acids at different concentrations. When 1 was
heated in propan-1-ol at 75 °C for 10 minutes without any
additive, the undesired products 9-methoxyanthracene
(2a) and anthracene (3) were obtained (entry 1, Table 1).
However, by including a Lewis acid at only the 0.01 to 0.5
SYNTHESIS 2009, No. 10, pp 1703–1707
x
x.
x
x
.
2
0
0
9
Advanced online publication: 30.04.2009
DOI: 10.1055/s-0028-1088073; Art ID: F25008SS
© Georg Thieme Verlag Stuttgart · New York

1704
K. S. Jang et al.
PAPER
mol% level, transetherification occurred to produce dif- even allyl alcohol reacted well. In case of primary alco-
ferent products (entries 2–4). The reaction was then car- hols, transetherification yields were 65–68%, which are
ried out using different Lewis acids also at 75 °C for 10 much higher than previously reported (entries 2–6).8,9,14
minutes, and with the exception of lanthanum(III) trifluo- When 2-methoxyethanol was used, transetherification
romethanesulfonate [La(OTf)3], transetherification yields gave the corresponding 9-(2-methoxyethoxy)anthracene
were reduced as acid concentrations were increased. In (2g) in good yield (73%, entry 7). On the other hand, when
addition, the side products 2a and 3 were produced re-
Table 2 Transetherification from trans-9,10-Dihydro-9,10-
gardless of reaction conditions. The reaction was also car-
dimethoxyanthracene (1) with Alcohols in the Presence of Sulfuric
ried out at a reaction temperature of 0 °C for 10 minutes
(entry 13). The intriguing result of the above exercise was
that 9-propoxyanthracene (2c) production was greatest in
the presence of sulfuric acid, which also produced lowest
levels of side products and only a trace amount of com-
pound 3 (Scheme 1).
Acida
OMe
OR
ROH
+
3
H2SO4, 75 °C
10 min
2a–p
OMe
Under optimized conditions (Table 1, entry 12, at 75 °C
for 10 minutes), the transetherifications of a variety of 9-
1
alkoxyanthracene derivatives 2a–v were attempted from 1 Entry Alcohol
Yield (%)b
(Table 2). Primary, secondary, cyclic alcohols, PEG, and
2a–v
2a
74
14
15
19
12
19
8
3
Table 1 Acids Screened for the Transetherification of trans-9,10-
Dihydro-9,10-dimethoxyanthracene (1) in Propan-1-ola
1
methanol
ethanol
– (2a)
68 (2b)
65 (2c)
67 (2d)
68 (2e)
65 (2f)
73 (2g)
25 (2h)
55 (2i)
57 (2j)
40 (2k)
44 (2l)
46 (2m)
65 (2n)
53 (2o)
22c (2p)
– (2q)
13
6
2c
3
OMe
propan-1-ol
butan-1-ol
pentan-1-ol
hexan-1-ol
trace
5
propan-1-ol
acid, 75 °C
10 min
4
OMe
5
7
1
6
8
OMe
O
7
2-methoxyethanol
1-bromoethanol
benzyl alcohol
allyl alcohol
5
+
+
8
trace
5
9c
15
13
12
21
28
23
19
10
63
30
47
29
62
68
5
2c
2a
3
Yield (%)b
10
6
Entry
Lewis acids (equiv)
2c
2a
74
15
15
25
30
26
21
23
12
13
18
15
35
3
11
12
13
14
15
16
17
18
19
20
21d
22d
ethylene glycol
propane-1,3-diol
butane-1,4-diol
triethylene glycol
isoamyl alcohol
propan-2-ol
15
12
9
1
2
none
–
13
13
10
2
FeCl3 (1.0)
29
30
42
42
47
44
34
32
34
45
65
30
3
FeCl3 (0.5)
4
4
FeCl3 (0.05)
AlCl3 (1.0)
11
1
5
3
6
La(OTf)3 (1.0)
La(OTf)3 (0.5)
La(OTf)3 (0.05)
Sc(OTf)3 (1.0)
Sc(OTf)3 (0.5)
Sc(OTf)3 (0.05)
H2SO4 (0.05)
H2SO4 (0.05)
5
tert-butanol
4
7
7
cyclopentanol
cyclohexanol
43 (2r)
37 (2s)
29 (2t)
8 (2u)
7
8
5
4
9
12
5
cycloheptanol
dihydrocholesterol
epiandrosterone
10
11
trace
10
11
12
13c
7
10 (2v)
trace
16
a All reactions were carried out using 0.5 mmol reaction scale of 1 in
2.0 mL of each alcohol in the presence of a catalytic amount of H2SO4
(2.0 L) at 75 °C for 10 min.
b Isolated yields.
a All reactions were carried out on a 0.5 mmol scale of 1 in 2.0 mL of
propan-1-ol at 75 °C for 10 min.
c NMR-determined yield.
d The reaction was carried out using 1.0 mmol of 1 in toluene (2.0
mL).
b Isolated yield.
c Reaction temperature was 0 °C.
Synthesis 2009, No. 10, 1703–1707 © Thieme Stuttgart · New York

PAPER
Synthesis of 9-Anthryl Ethers by Acid-Catalyzed Transetherification
1705
appropriate alcohol (2.0 mL). This mixture was then heated at 75 °C
for 10 min, cooled to r.t., and extracted with EtOAc (3 × 10 mL) and
H2O (10 mL). The combined organic layers were dried (Na2SO4),
concentrated, and purified by flash column chromatography (30%
CH2Cl2–hexane).
1-bromoethanol was used, we obtained the desired prod-
uct 2h in only 25% yield (entry 8). Furthermore, when
benzyl alcohol (entry 9) was used, the product 2i was not
obtained in a pure form because of its poor stability. How-
ever, reaction with allyl alcohol produced the desired
product 2j, and this was stable enough to be isolated in a
pure form at a yield of 57% (entry 10). The reaction was
also performed using four diols (entries 11–14), to see
whether intramolecular-annulated crown ether of an-
thracene at C9 and C10-position formed or not. However,
when triethylene glycol was used (entry 14), only 9-
alkoxyanthracene (2n) was achieved as usual (65%). The
transetherification of 1 with isoamyl alcohol, propan-2-ol,
or tert-butanol (entries 15–17, Table 2) suggested that the
course of the reaction is influenced by steric effects. In
contrast to the primary alcohols, as mentioned above (en-
tries 2–6, Table 2), transetherification with propan-2-ol
produced 9-isopropoxyanthracene (2p) in 22% yield, and
tert-butanol formed 9-methoxyanthracene (3) in high
yield (63%) rather than 9-(tert-butoxy)anthracene (2q).
9-Methoxyanthracene (2a)
Pale yellow solid; mp 93.2–93.3 °C.
1H NMR (400 MHz, CDCl3): d = 4.16 (s, 3 H), 7.46–7.51 (m, 4 H),
7.99 (dd, J = 7.2, 2.0 Hz, 2 H), 8.23 (s, 1 H), 8.30 (d, J = 6.8 Hz, 1
H), 8.31 (d, J = 1.6 Hz, 1 H).
13C NMR (100 MHz, CDCl3): d = 63.2, 122.2, 122.3, 124.4, 125.2,
125.5, 128.4, 132.4, 152.2.
MS (EI): m/z (%) = 208 [M+], 193 (100), 176, 165, 163, 139, 115,
104.
HRMS (EI): m/z calcd for C15H12O [M+]: 208.0888; found:
208.0890.
Registry No. 2395-96-2.
9-n-Propoxyanthracene (2c)
Yield: 65%; white solid; mp 75.5–77.6 °C.
1H NMR (400 MHz, CDCl3): d = 1.24 (t, J = 7.4 Hz, 3 H), 2.07–2.12
(m, 2 H), 4.18 (t, J = 6.8 Hz, 2 H), 7.45–7.50 (m, 4 H), 7.98–8.01
(m, 2 H), 8.22 (s, 1 H), 8.30–8.33 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 10.7, 23.9, 77.6, 121.9, 122.4,
124.7, 125.0, 125.4, 128.4, 132.4, 151.4.
MS (EI): m/z (%) = 236 [M+], 194 (100), 165, 139.
HRMS (EI): m/z calcd for C17H16O [M+]: 236.1201; found:
Acid-catalyzed transetherification using cyclic alcohols,
such as cyclopentanol, cyclohexanol, and cycloheptanol
provided 2r, 2s, and 2t (entries 18–20), respectively. The
preparation of 9-anthryl cyclopentyl ether 2r was
achieved by the Buchwald group via the palladium-cata-
lyzed intermolecular coupling of 9-bromoanthracene and
cyclopentanol in 48% yield.15 This method is also useful
for producing anthryl ethers via palladium-catalyzed in-
termolecular carbon–oxygen bond formation. The other
two compounds 2s and 2t have not been previously syn-
thesized. Finally, the application of this methodology to
dihydrocholesterol and epiandrosterone afforded the de-
sired transetherification products 2u,v in low yields (8 and
10%, respectively), which was expected based on steric
considerations, in addition to the undesired byproducts (3
and 2a).
236.1204.
Registry No. 92830-42-7.
9-n-Butoxyanthracene (2d)
Yield: 67%; white solid; mp 87.1–87.7 °C.
1H NMR (400 MHz, CDCl3): d = 1.11 (t, J = 7.4 Hz, 3 H), 1.70–
1.79 (m, 2 H), 2.04–2.11 (m, 2 H), 4.24 (t, J = 6.6 Hz, 2 H), 7.55–
7.46 (m, 4 H), 8.02–8.00 (m, 2 H), 8.23 (s, 1 H), 8.36–8.32 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 14.1, 19.5, 32.7, 75.9, 121.9,
122.4, 124.7, 125.0, 125.4, 128.4, 132.4, 151.5.
In summary, we describe the synthesis of 9-anthryl ethers
via the acid-catalyzed transetherification of trans-9,10-di-
hydro-9,10-dimethoxyanthracene with different alcohols.
This devised transetherification method was found to be
more efficient than any other reported procedure for the
preparation of 9-alkoxyanthracene from trans-9,10-dihy-
dro-9,10-dimethoxyanthracene (1). It is hoped that this
convenient and selective transetherification will be found
to be a generally useful method for the preparation of a va-
riety of 9-alkoxyanthracenes.
MS (EI): m/z (%) = 250 [M+], 194 (100), 165, 139.
HRMS (EI): m/z calcd for C18H18O [M+]: 250.1358; found:
250.1359.
Registry No. 92830-43-8.
9-n-Pentoxyanthracene (2e)
Yield: 68%; pale yellow solid; mp 55.7–56.8 °C.
1H NMR (400 MHz, CDCl3): d = 1.03 (t, J = 8.4 Hz, 3 H), 1.48–
1.54 (m, 2 H), 1.66–1.70 (m, 2 H), 2.07–2.14 (m, 2 H), 4.22 (t,
J = 7.4 Hz, 2 H), 7.45–7.52 (m, 4 H), 7.99–8.02 (m, 2 H), 8.22 (s, 1
H), 8.31–8.33 (m, 2 H).
All chemicals were purchased from commercial sources (Sigma-
Aldrich, TCI, Acros) and used without further purification. Analyt-
ical TLC was carried out on pre-coated plates (Merck, silica gel
60F254). Flash column chromatography was performed with silica
gel (Merck, 230–400 mesh, ASTM). 1H NMR and 13C NMR spectra
were recorded on Varian 400-MR (400 MHz) and Varian Gemini
2000 (200 MHz) spectrometers at ambient temperature. Mass spec-
tra were obtained on an HP590 GC/MS 5972 MSD spectrometer.
13C NMR (100 MHz, CDCl3): d = 14.1, 22.7, 28.4, 30.4, 76.2, 121.9,
122.4, 124.7, 125.0, 125.4, 128.4, 132.4, 151.5.
MS (EI): m/z (%) = 264 [M+], 194 (100), 165, 139.
HRMS (EI): m/z calcd for C19H20O [M+]: 264.1514; found:
264.1513.
Registry No. 112607-81-5.
9-n-Hexoxyanthracene (2f)
Yield: 65%; yellow solid; mp 42.4–43.7 °C.
9-Anthryl Ethers; General Procedure
A catalytic amount of H2SO4 (2.0 L) was added to a solution of
trans-9,10-dihydro-9,10-dimethoxyanthracene (1, 0.5 mmol) in an
Synthesis 2009, No. 10, 1703–1707 © Thieme Stuttgart · New York

1706
K. S. Jang et al.
PAPER
1H NMR (400 MHz, CDCl3): d = 0.96 (t, J = 5.2 Hz, 3 H), 1.42–
1.66 (m, 4 H), 1.66–1.69 (m, 2 H), 2.04–2.08 (m, 2 H), 4.20 (t,
J = 6.6 Hz, 2 H), 7.44–7.50 (m, 4 H), 7.98–8.01 (m, 2 H), 8.22 (s, 1
H), 8.29–8.31 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 14.1, 22.7, 25.9, 30.6, 31.8, 76.2,
121.9, 122.4, 124.7, 125.0, 125.4, 128.4, 132.4, 151.5.
9-(3-Hydroxy-n-propoxy)anthracene (2l)
Yield: 44%; pale yellow solid; mp 89.3–90.9 °C.
1H NMR (400 MHz, CDCl3): d = 2.24 (br s, 1 H), 2.29–2.32 (m, 2
H), 4.15 (t, J = 5.8 Hz, 2 H), 4.36 (t, J = 6.0, 2 H), 7.45–7.51 (m, 4
H), 7.98–8.01 (m, 2 H), 8.23 (s, 1 H), 8.28–8.31 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 33.1, 61.2, 74.1, 122.1, 122.4,
124.6, 125.3, 125.5, 128.5, 132.4, 150.8.
MS (EI): m/z (%) = 278 [M+], 194 (100), 165, 139.
HRMS (EI): m/z calcd for C20H22O [M+]: 278.1671; found:
MS (EI): m/z (%) = 252 [M+], 194 (100), 165, 152, 129.
278.1673.
HRMS (EI): m/z calcd for C17H16O2 [M+]: 252.1150; found:
Registry No. 1126-82-6.
252.1150.
9-(2-Methoxyethoxy)anthracene (2g)
Yield: 73%; white solid; mp 106.9–108.1 °C.
9-(4-Hydroxy-n-butoxy)anthracene (2m)
Yield: 46%; white solid; mp 72.1–74.5 °C.
1H NMR (400 MHz, CDCl3): d = 3.59 (s, 3 H), 3.91 (t, J = 4.6 Hz,
2 H), 4.37 (t, J = 4.6 Hz, 2 H), 7.45–7.52 (m, 4 H), 7.98–8.01 (m, 2
H), 8.24 (s, 1 H), 8.31–8.39 (m, 2 H).
1H NMR (400 MHz, CDCl3): d = 1.94–2.01 (m, 3 H), 2.10–2.17 (m,
2 H), 3.83 (t, J = 6.4 Hz, 2 H), 4.22 (t, J = 6.4 Hz, 2 H), 7.44–7.51
(m, 4 H), 7.98–8.00 (m, 2 H), 8.21 (s, 1 H), 8.27–8.30 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 59.7, 72.3, 75.0, 122.7, 122.8,
125.0, 125.5, 125.8, 128.7, 132.7, 151.1.
13C NMR (100 MHz, CDCl3): d = 27.2, 29.7, 62.8, 75.8, 122.1,
122.3, 124.6, 125.1, 125.4, 128.4, 132.4, 151.1.
MS (EI): m/z (%) = 252 [M+], 194 (100), 165, 139, 115.
MS (EI): m/z (%) = 266 [M+], 208, 194 (100), 165, 152, 129.
HRMS (EI): m/z calcd for C17H16O2 [M+]: 252.1150; found:
HRMS (EI): m/z calcd for C18H18O2 [M+]: 266.1307; found:
252.1152.
266.1305.
Registry No. 112607-85-9.
9-(8-Hydroxy-3,6-dioxaoctoxy)anthracene (2n)
Yield: 65%; yellow solid; mp 44.6–46.2 °C.
9-(2-Bromoethoxy)anthracene (2h)
Yield: 25%; white solid; mp 112.3–115.3 °C.
1H NMR (200 MHz, CDCl3): d = 3.03 (br s, 1 H), 3.64–3.68 (m, 2
H), 3.75–3.80 (m, 6 H), 3.93–3.97 (m, 2 H), 4.33–4.37 (m, 2 H),
7.40–7.53 (m, 4 H), 7.93–7.98 (m, 2 H), 8.19 (s, 1 H), 8.36–8.41 (m,
2 H).
13C NMR (50 MHz, CDCl3): d = 61.6, 70.3, 70.4, 70.7, 72.5, 74.5,
122.2, 122.3, 124.5, 125.1, 125.3, 128.2, 132.2, 150.6.
MS (EI): m/z (%) = 326 [M+], 208 (100), 180, 152, 119.
HRMS (EI): m/z calcd for C20H22O4 [M+]: 326.1518; found:
1H NMR (400 MHz, CDCl3): d = 3.87 (t, J = 6.0 Hz, 2 H), 4.53 (t,
J = 6.2 Hz, 2 H), 7.47–7.53 (m, 4 H), 7.99–8.02 (m, 2 H), 8.26 (s, 1
H), 8.34–8.37 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 30.4, 74.7, 122.0, 122.7, 124.5,
125.45, 125.47, 128.4, 132.2, 149.8.
MS (EI): m/z (%) = 302 [M+], 300 [M+], 193 (100), 165, 139, 115.
HRMS (EI): m/z calcd for C16H13BrO [M+]: 300.0150; found:
326.1521.
300.0148.
Registry No. 86129-58-0.
9-Isoamyloxyanthracene (2o)
Yield: 53%; white solid; mp 63.9–65.3 °C.
9-Allyloxyanthracene (2j)
Yield: 57%; yellow solid; mp 95.9–97.1 °C.
1H NMR (400 MHz, CDCl3): d = 4.75–4.77 (m, 2 H), 5.38–5.41 (m,
1 H), 5.59–5.64 (m, 1 H), 6.29–6.39 (m, 1 H), 7.46–7.52 (m, 4 H),
7.99–8.03 (m, 2 H), 8.24 (s, 1 H), 8.31–8.35 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 76.4, 117.6, 122.2, 122.3, 124.7,
125.1, 125.4, 128.3, 132.3, 133.8, 150.9.
MS (EI): m/z (%) = 234 [M+], 193 (100), 165, 163, 139, 115.
HRMS (EI): m/z calcd for C17H14O [M+]: 234.1045; found:
1H NMR (400 MHz, CDCl3): d = 1.03 (d, J = 6.4 Hz, 6 H), 1.92–
1.98 (m, 2 H), 2.00–2.05 (m, 1 H), 4.20 (t, J = 6.6 Hz, 2 H), 7.41–
7.47 (m, 4 H), 7.95–7.98 (m, 2 H), 8.19 (s, 1 H), 8.25–8.28 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 22.8, 25.2, 39.5, 74.7, 121.9,
122.5, 124.7, 125.0, 125.4, 128.4, 132.5, 151.6.
MS (EI): m/z (%) = 264 [M+], 194 (100), 178, 165, 151.
HRMS (EI): m/z calcd for C19H20O [M+]: 264.1514; found:
264.1517.
234.1045.
9-Cyclopentoxyanthracene (2r)
Yield: 43%; yellow solid; mp 77.7–79.1 °C.
Registry No. 125340-11-6.
1H NMR (400 MHz, CDCl3): d = 1.69–1.85 (m, 4 H), 2.06–2.19 (m,
4 H), 4.92–4.95 (m, 1 H), 7.43–7.50 (m, 4 H), 7.97–8.00 (m, 2 H),
8.20 (s, 1 H), 8.29–8.32 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 24.1, 33.4, 88.6, 122.1, 123.4,
125.1, 125.6, 125.7, 128.7, 132.8, 151.2.
MS (EI): m/z (%) = 262 [M+], 194 (100), 165, 139, 115.
HRMS (EI): m/z calcd for C19H18O [M+]: 262.1357; found:
9-(2-Hydroxyethoxy)anthracene (2k)
Yield: 40%; yellow solid; mp 106.2–108.2 °C.
1H NMR (400 MHz, CDCl3): d = 2.80 (br s, 1 H), 4.17 (t, J = 4.4
Hz, 2 H), 4.31 (t, J = 4.4 Hz, 2 H), 7.45–7.48 (m, 4 H), 7.97–8.00
(m, 2 H), 8.22 (s, 1 H), 8.32–8.35 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 62.4, 76.5, 122.0, 122.5, 124.5,
125.3, 125.4, 128.4, 132.3, 150.3.
MS (EI): m/z (%) = 238 [M+], 194 (100), 165, 151, 115.
HRMS (EI): m/z calcd for C16H14O2 [M+]: 238.0994; found:
262.1358.
Registry No.188527-60-8.
238.0990.
9-Cyclohexoxyanthracene (2s)
Yield: 37%; yellow solid; mp 104.3–106.2 °C.
Registry No. 86129-59-1.
Synthesis 2009, No. 10, 1703–1707 © Thieme Stuttgart · New York

PAPER
Synthesis of 9-Anthryl Ethers by Acid-Catalyzed Transetherification
1707
1H NMR (400 MHz, CDCl3): d = 1.19–1.28 (m, 3 H), 1.59–1.61 (m,
1 H), 1.72–1.84 (m, 4 H), 2.10–2.14 (m, 2 H), 4.21–4.26 (m, 1 H),
7.43–7.47 (m, 4 H), 7.96–7.99 (m, 2 H), 8.19 (s, 1 H), 8.31–8.33 (m,
2 H).
13C NMR (100 MHz, CDCl3): d = 24.8, 25.6, 33.5, 84.3, 121.6,
123.1, 124.6, 125.2, 125.5, 128.2, 132.3, 150.1.
mmol). A white solid (23 mg; 10%) was obtained; mp 206.6–
208.3 °C.
1H NMR (400 MHz, CDCl3): d = 0.50–0.63 (m, 1 H), 0.78–1.09 (m,
8 H), 1.11–1.33 (m, 4 H), 1.39–1.61 (m, 4 H), 1.69–1.85 (m, 6 H),
1.89–2.11 (m, 4 H), 2.35–2.48 (m, 1 H), 4.12–4.33 (m, 1 H), 7.40–
7.49 (m, 4 H), 7.95–7.99 (m, 2 H), 8.19 (s, 1 H), 8.29–8.34 (m, 2 H).
MS (EI): m/z (%) = 276, 194 (100), 165, 139, 115.
HRMS (EI): m/z calcd for C20H20O [M+]: 276.1514; found:
276.1516.
13C NMR (100 MHz, CDCl3): d = 12.4, 13.8, 20.4, 21.7, 28.3, 29.1,
30.8, 31.5, 34.9, 35.4, 35.8, 36.9, 44.9, 47.7, 51.3, 54.3, 84.6, 121.7,
123.1, 124.7, 125.3, 125.6, 128.3, 132.3, 150.2, 221.2.
MS (EI): m/z (%) = 466 [M+], 429, 384, 355, 290, 223, 194 (100),
9-Cycloheptoxyanthracene (2t)
180, 152, 107.
Yield: 29%; yellow solid; mp 90.6–93.1 °C.
HRMS (EI): m/z calcd for C33H38O2 [M+]: 466.2872; found:
466.2872.
1H NMR (400 MHz, CDCl3): d = 1.31–1.40 (m, 2 H), 1.56–1.65 (m,
4 H), 1.75–1.81 (m, 2 H), 1.95–2.04 (m, 2 H), 2.11–2.19 (m, 2 H),
4.45–4.52 (m, 1 H), 7.42–7.48 (m, 4 H), 7.95–7.99 (m, 2 H), 8.19
(s, 1 H), 8.27–8.31 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 22.8, 28.5, 34.6, 86.8, 121.6,
123.2, 124.6, 125.3, 125.6, 128.3, 132.4, 150.3.
Supporting Information for this article is available online at
http://www.thieme-connect.com/ejournals/toc/synthesis.
MS (EI): m/z (%) = 290 [M+], 194 (100), 178, 165, 152, 139.
Acknowledgment
HRMS (EI): m/z calcd for: C21H22O [M+]: 290.1671; found:
290.1666.
This work was supported by a Korea Science and Engineering
Foundation (KOSEF) grant. High resolution mass spectroscopy was
carried out at the Korea Basic Science Institute.
3-(O-Anthracen-9-yl)-3a,5a-dihydrocholestane (2u); Typical
Procedure
References
A catalytic amount of H2SO4 (3.0 L) and solution of 3a,5a-dihydro-
3-cholesterol (194 mg, 0.5 mmol) in toluene (1 mL) was added to a
solution of trans-9,10-dihydro-9,10-dimethoxyanthracene (0.5
mmol) in toluene (1.0 mL). The mixture was then heated at 75 °C
for 10 min, cooled to r.t., and extracted with EtOAc (3 × 10 mL) and
H2O (10 mL). The combined organic layers were dried (Na2SO4),
concentrated, and purified by flash column chromatography (30%
CH2Cl2–hexane), to provide 2u as a white solid (22 mg; 8%); mp
239.4–240.9 °C.
1H NMR (400 MHz, CDCl3): d = 0.64 (s, 2 H), 0.84–0.89 (m, 10 H),
0.91–0.97 (m, 5 H), 0.99–1.11 (m, 8H), 1.17–1.35 (m, 10 H), 1.42–
1.63 (m, 4 H), 1.69–1.83 (m, 4 H), 1.92–2.17 (m, 3 H), 4.24–4.27
(m, 1 H), 7.43–7.46 (m, 4 H), 7.96–7.99 (m, 2 H), 8.19 (s, 1 H),
8.30–8.33 (m, 2 H).
13C NMR (100 MHz, CDCl3): d = 12.4, 12.9, 19.0, 21.6, 22.9, 23.2,
24.1, 24.5, 28.3, 28.6, 29.1, 29.5, 32.4, 35.77, 35.84, 36.0, 36.1,
36.5, 37.4, 39.8, 40.3, 42.9, 45.3, 54.6, 56.5, 56.7, 85.3, 122.0,
123.6, 125.1, 125.7, 125.9, 128.6, 132.7, 150.6.
MS (EI): m/z (%) = 564 [M+], 549, 508, 479, 449, 438, 402, 371,
355, 316, 275, 257, 231, 215, 194 (100), 165, 135.
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HRMS (EI): m/z calcd for C41H56O [M+]: 564.4331; found:
564.4331.
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3-(O-Anthracen-9-yl)-3b,5a-androstanone (2v)
Compound 2v was prepared using a similar procedure as that de-
scribed above for 2u from 3b,5a-androstanon-3-ol (143 mg, 0.5
Synthesis 2009, No. 10, 1703–1707 © Thieme Stuttgart · New York