A. Kertmen et al. / Tetrahedron 69 (2013) 10662e10668
10667
bottomed flask and stirred. Thionyl chloride (78 mmol) was added to
mixture. Then stannous chloride dihydrate (7 mmol, 1.58 g) was
added to the mixture. After the strongly exothermic reaction
ceased, the reaction was refluxed at 70 C for 3 h.
ꢁ
the flask dropwise at 0 C over 30 min. The mixture was refluxed at
ꢁ
ꢁ
7
0 C for 2 h. After the solvent was evaporated in vacuo, the residue
was mixed with benzene and filtered under vacuum to remove the
deposited pyridine hydrochloride. The benzene solution was washed
with water and the benzene layer containing the title compound was
isolated which subsequently evaporated in vacuo.
In the case of crown ethers 4-a, 5-a and 4-c, 5-c, the resulting
precipitate was removed by filtration in vacuo and washed with
acetone. After the evaporation of acetone in vacuo, resulting
products were purified by column chromatography using methy-
lene chloride as eluent.
3
.3.1. 1,2-Bis(2-chloroethoxy)benzene (2-a). Compound (2-a) was
In the case of naphthalene substituted crown ethers 4-b and 5-
b, toluene was added to the cooled reaction mixture and the pre-
cipitated sodium chloride was removed by filtration in vacuo. Fil-
tered NaCl was washed with toluene and the filtrates were
combined. After washing the filtrates with water, the organic layer
was separated and evaporated in vacuo. Resulting crude, dark
brown product was chromatographed on silica gel column using
firstly methylene chloride and then a mixture of methylene chlor-
ideemethanol (10:1) as the eluent.
obtained as a white solid after recrystallization from methanol,
ꢁ
18
ꢁ
1
yield: 38%, mp 52e56 C (lit. mp: 50e52 C). H NMR (500 MHz,
);
DMSO): 3.68 (4H, t, J¼4.45 Hz, OCH
2
); 3.96 (4H, t, J¼4.43 Hz, CH
2
6
.90e7.10 (3H, m, ArH); 7.26 (1H, s, ArH).
3.3.2. 2,3-Bis(2-chloroethoxy)naphthalene (2-b). Compound (2-b)
was obtained as a pale brown solid after recrystallization from
ꢁ
19
ꢁ
1
methanol yield: 34.5%, mp: 94e96 C (lit. mp: 90e92 C). H NMR
500 MHz, DMSO): 3.80e4.10 (4H, m, OCH ); 4.20e4.40 (4H, m,
CH ); 7.20e7.50 (4H, m, ArH); 7.60e7.80 (2H, m, ArH).
(
2
2
3.5.1. Azocrown ether (4-a). Compound (4-a) was obtained as an
ꢁ
1
orange solid in 12% yield, mp: 155e158 C. H NMR (500 MHz,
DMSO): 3.35 (2H, t, J¼5.37 Hz, SCH ); 3.41 (2H, t, J¼5.37 Hz, SCH );
4.20e4.23 (4H, m, OCH ); 6.84e6.88 (2H, m, ArH); 6.96e7.0 (2H, m,
0
0
3.3.3. 2,2 -Bis(2-chloroethoxy)-1,1 -binaphthalene (2-c). Compound
2
2
(2-c) was obtained as a white solid after crystallization from
2
ꢁ
17
ꢁ
1
methanol, yield: 22.3%, mp 100e103 C (lit. mp: 100e103 C). H
NMR (200 MHz, DMSO): 3.39 (4H, t, J¼6.27 Hz, OCH ); 4.10e4.30
4H, m, CH ); 7.10e7.50 (8H, m, ArH); 7.80e8.05 (4H, m, ArH).
ArH); 7.25e7.28 (1H, m, ArH); 7.32e7.38 (2H, m, ArH); 7.54e7.58
2
(2H, m, ArH); 7.60e7.64 (1H, m, ArH); 7.90e7.96 (2H, m, ArH);
þ
(
2
HRMS (EI) M found 424.1487. C22
(
20
H N
2
O
2
S
2
requires 408.1566. IR
ꢀ1
film): 2965, 1600, 1550, 1430, 1360, 1100, 760 cm .
3
.4. General procedure for the syntheses of 3-a,b,c
Separately, each of the compounds 2-a, 2-b or 2-c (4.5 mmol)
3
.5.2. Azoxycrown ether (5-a). Compound (5-a) was obtained as
ꢁ
1
a yellow solid in 20% yield, mp: 146e148 C. H NMR (500 MHz,
DMSO): 3.36e3.42 (4H, m, SCH ); 4.15e4.25 (4H, m, OCH );
was added into a solution of o-nitrothiophenol (9 mmol, 1.4 g) in
2
2
DMF, in the presence of anhydrous potassium carbonate (9 mmol,
6.82e6.90 (2H, m, ArH); 6.94e7.0 (2H, m, ArH); 7.22e7.30 (1H, m,
ArH); 7.32e7.38 (2H, m, ArH); 7.52e7.58 (2H, m, ArH); 7.60e7.64
ꢁ
1.24 g) and stirred for 20 h at 70 C. After cooling, the reaction
mixture was diluted with ice-water. Upon the addition of water, the
precipitate was obtained. The precipitate was isolated by filtration
and washed with water.
(1H, m, ArH); 7.88e7.90 (1H, m, ArH); 8.10e8.12 (1H, m, ArH);
þ
HRMS (EI) M found 408.1623. C22
H
20
N
2
O
3
S
2
requires 424.15153. IR
ꢀ
1
(film): 2940, 1630, 1520, 1460, 1400, 1160, 1150, 750 cm
.
3
.4.1. 1,2-Bis(2-(2-nitrophenylthio)ethoxy)benzene (3-a). Compound
3.5.3. Azocrown ether (4-b). Compound (4-b) was obtained as an
ꢁ
1
(3-a) was obtained from 2-a as a yellow solid after recrystallization
orange solid in 30% yield, mp: 188e190 C. H NMR (500 MHz,
);
ꢁ
1
from methanol. Yield: 58%, mp 138e143 C. H NMR (200 MHz,
DMSO): 3.45 (4H, t, J¼6.23 Hz, SCH ); 4.23e4.28 (4H, m, OCH );
.89e7.0 (4H, m, ArH); 7.30e7.45 (2H, m, ArH); 7.60e7.80 (4H, m,
DMSO): 3.53 (4H, t, J¼6.35 Hz, SCH
2
); 4.35 (4H, t, J¼6.35 Hz, OCH
2
2
2
7.28e7.32 (3H, m, ArH); 7.36e7.40 (3H, m, ArH); 7.68e7.74 (4H, m,
6
ArH); 7.78e7.81 (3H, m, ArH); 8.14e8.18 (1H, m, ArH); HRMS (EI)
þ
þ
ArH); 8.10e8.20 (2H, m, ArH). HRMS (EI) M found 472.5022.
requires 472.5016. IR (film) 2980, 1610, 1555, 1345,
M
22 2 2 2
found 458.1668. C26H N O S requires 458.1722. IR (film):
ꢀ1
C
H N O S
22 20 2 6 2
2970, 1500, 1470, 1290, 1140, 1100, 750 cm
.
ꢀ
1
1230, 1095, 851, 750 cm
.
3
.5.4. Azoxycrown ether (5-b). Compound (5-b) was obtained in
ꢁ
1
3.4.2. 2,3-Bis[2-(2-nitrophenylthio)ethoxy]naphthalene
(3-b).
10% yield, mp 174e177 C. H NMR (500 MHz, DMSO): 3.45 (2H, t,
J¼5.37 Hz, SCH ); 3.51 (2H, t, J¼5.38 Hz, SCH ); 4.32e4.40 (4H, m,
OCH ); 7.21e7.38 (6H, m, ArH); 7.52e7.58 (2H, m, ArH); 7.60e7.62
Compound (3-b) was obtained from 2-b as a yellow solid. Yield:
2
2
ꢁ
1
7
5.7%, mp 172e175 C. H NMR (200 MHz, DMSO): 3.54 (4H, t,
); 7.27e7.45 (6H, m,
2
J¼6.23 Hz, SCH
2
); 4.36 (4H, t, J¼6.31 Hz, OCH
2
(2H, m, ArH); 7.63e7.67 (2H, m, ArH); 7.83e7.87 (2H, m, ArH).
þ
ArH); 7.53e7.90 (6H, s, ArH); 8.10e8.20 (2H, m, ArH). HRMS (EI)
HRMS (EI) M found 474.1655. C26
22
H N
2
O
3
S
2
requires 474.1671. IR
þ
ꢀ1
M
3
found 522.5558. C26
H
22
N
2
O
6
S
2
requires 522.5603. IR (film)
(film): 12,960, 1625, 1500, 1470, 1390, 1140, 1100, 750 cm
.
ꢀ1
000, 1610, 1524, 1349, 1220, 1130, 860, 753 cm .
3
.5.5. Azocrown ether (4-c). Compound (4-c) was obtained in 28%
0
0
ꢁ
1
3
.4.3. 2,2 -Bis[2-(2-nitrophenylthio)ethoxy]-1,1 -binaphthalene (3-
yield, mp: 178e181 C. H NMR (500 MHz, DMSO): 3.50e3.52 (4H,
m, SCH ); 4.20e4.35 (4H, m, OCH
7.16e7.24 (4H, m, ArH); 7.28e7.38 (6H, m, ArH); 7.40e7.42 (2H, m,
ArH); 7.50e7.60 (2H, m, ArH); 7.80e7.95 (4H, m, ArH). HRMS (EI)
M
c). Compound (3-c) was obtained from 2-c as a yellow solid. Yield
2
2
); 6.90 (2H, t, J¼7.32 Hz, ArH);
ꢁ
1
5
4.6%, mp: 158e160 C H NMR (200 MHz, DMSO):3.50e3.52(4H, m,
SCH ); 4.20e4.35 (4H, m, OCH ); 6.80e7.0 (2H, m, ArH); 7.15e7.45
8H, m, ArH); 7.52e7.70 (4H, m, ArH); 7.90e8.10 (6H, m, ArH). HRMS
EI) M found 472.5022. C22
880, 1625, 1550, 1345, 1340, 1240, 1100, 850, 760 cm .
2
2
þ
(
(
2
found 584.2146. C36
H
28
N
2
O
S
2 2
requires 584.2192. IR (film):
þ
ꢀ1
H N O S
20 2 6 2
requires 472.5016. IR (film)
2960, 1600, 1500, 1450, 1360, 1180, 1050, 740 cm
.
ꢀ
1
3
.5.6. Azoxycrown ether (5-c). Compound (5-c) was obtained in
ꢁ
1
3
.5. General procedure for the syntheses of 4-a,b,c and 5-a,b,c
12% yield, mp 102e107 C H NMR (500 MHz, DMSO): 3.52e3.54
4H, m, SCH ); 4.25e4.35 (4H, m, OCH ); 6.84e6.92 (2H, m, ArH);
(
2
2
Separately, each of the dinitro-derivatives 3-a, 3-b, 3-c (2 mmol)
7.12e7.22 (4H, m, ArH); 7.26e7.32 (6H, m, ArH); 7.42e7.46 (2H, m,
was suspended in a mixture of acetone and water (1:1) in a round
bottomed flask and NaOH (60 mmol, 2.39 g) was dissolved in the
ArH); 7.52e7.56 (1H, m, ArH); 7.82e7.98 (4H, m, ArH); 8.10e8.15
þ
(1H, m, ArH). HRMS (EI) M found 600.2201. C36
H
28
N
2
O
3
S
2
requires