506
U. Calisir, B. Çiçek / Journal of Molecular Structure 1148 (2017) 505e511
when replacing sulphur, oxygen, phenyl, and carbonyl chromo-
sphere with each other [24].
under a nitrogen atmosphere in StartSYNTH-Microwave Synthesis
ꢀ
Labstation system. (MW, E¼1000 W, 100 C), then left to cool to
As part of this study, novel benzo-thio crown ethers were syn-
thesised using a high dilution method and microwave-assisted
synthesis method. These synthesised ligands contain different
ring cavities due to ligands and heteroatoms (S and O). Above all,
their selectivity for complexation with alkaline, alkaline earth, and
transition metal cations is important in determining the strength of
ion-dipole interactions formed with cations, and assessing their
molecular dynamic [25]. The object of the present work is to study
room temperature.
General Work-up Procedure: The resultant mixture was evapo-
rated under vacuum. Distilled water (30e40 mL) was poured onto
the remaining residue, which was then extracted with organic
solvent (chloroform, 3 ꢂ 10 mL). The combined extracts were dried
2
with anhydrous CaCl , evaporated under vacuum, and purified by
silica gel column chromatography, to afford an oily solid product.
2,3,11,14,22,23,31,34-octathiapentacyclo
1
21
2 2
the extractive behaviour of LiCl, AgNO
CoCl , Pb(NO , CdCl , MgCl , NiCl , CaCl
bis(1,2-dibenzo) octathio tetracarbonil-24-crown-4), U2 (bis(1,2-
3
, ZnCl
2
, FeCl
3
, FeCl
2
, CrCl
3
,
[34.4.0.0⁴,⁹.0 ⁶, .0 ⁴, ⁹]tetraconta-
2
3
)
2
2
2
2
2
, NaCl, and KCl with U1
1(36),4(9),5,7,16,18,20,24,26,28,37,39-dodecaene-10,15,30,35-
tetrone (U1). Prepared with 1,2-ethanedithiol to the general
procedure-1 (1.0800 g, 11.45 mmol; 7 days) and general procedure-
2 (0.2386 g, 2.53 mmol, 1 h). Purification by column chromatog-
raphy (chloroform/ethyl acetate, 4:1, v/v) afforded a dark yellow-
(
dibenzo) octathio tetracarbonil-29-crown-6), U3 (bis(1,2-dibenzo)
octathio tetracarbonil-36-crown-8), U4 (bis(1,2-dibenzo) tetrathio
tetracarbonil-24-crown-4), U5 (bis(1,2-dibenzo) tetrathio tetra-
carbonil-29-crown-6), U6 (bis(1,2-dibenzo) tetrathio tetracarbonil-
brown oily product (3.4500 g, 36%; 1.4018 g, 76%, MW). FT-IR (
g
ꢁ1
3
6-crown-8), and U7 (bis(1,2-dibenzo) tetrathio tetracarbonil-42-
cm ) 1700 (O]CeS stretch), 1251 (SeC(O)eC stretch), 1053 (CeS
ꢀ
1
crown-10) in chloroform/water (1:1) at 25 C. The formation of
3
stretch); H NMR (CDCl , 400 MHz) d 4.41 (s, 8H), 7.22 (t, 4H,
1
:1 complexes of the metal-ions and electrically neutral crown
J¼8.0 Hz), 7.42 (t, 4H, J¼8.0 Hz), 7.78 (d, 4H, J¼8.0 Hz), 8.10 (d, 4H,
13 1
ethers was indicated.
J¼8.0 Hz); C{ H} NMR (CDCl
3
, 100 MHz)
d
29.80, 131.50, 131.80,
þ
1
32.20, 132.30, 132.60, 137.00, 166.20; LC-MS m/z 730 (M , CH
3
CN,
2
. Materials and methods
Error % ¼ ꢁ0.2830). Anal. Calc. for C32
2.72; H, 3.32; S, 35.19%. Found: C, 52.65; H, 3.26; S, 35.12%.
14,37-dioxa-2,3,11,17,25,26,34,40-octathiapentacyclo
[40.4.0.0⁴,⁹.0 ⁹, ⁴.0 ⁷, ]hexatetraconta-
1(42),4(9),5,7,19,21,23,27,29,31,43,45-dodecaene-10,18,33,41-
tetrone (U2). Prepared with diethylene glycol dithiol to the general
procedure-1 (1.7456 g, 11.45 mmol; 7 days) and general procedure-
2 (0.3857 g, 2.53 mmol, 1 h). Purification by column chromatog-
raphy (chloroform/hexane, 10:1, v/v) afforded a dark-brown oily
H
24
O
4
S
8
(MW¼729.05): C,
5
All chemicals used in this study, including analytical purity
1
2
2 32
solvents and reagents, were purchased from Merck, Sigma-Aldrich,
and Fluka Company. The StartSYNTH-Microwave Synthesis Lab-
station system were used to perform some reactions. Silica gel
column chromatography was applied for chromatographic purifi-
1
cations. FT-IR spectra were recorded on a Perkin Elmer BX 2 FTIR. H
NMR (400 MHz) and 13C NMR (100 MHz) spectra were obtained in
ꢁ
1
CDCl
3
or CD
3
OD solvents using NMR spectrometer. LC-MS spectra
solid (1.6895 g, 18%; 0.7443 g, 36%, MW). FT-IR (
CeS stretch), 1251 (SeC(O)eC stretch), 1053 (CeS stretch); HNMR
(CDCl , 400 MHz)
2.86 (s, 8H), 4.28 (s, 8H), 7.24 (t, 4H, J¼8.0 Hz),
g cm ) 1700 (O]
1
were recorded on the 2001 AB SCIEX Mass Spectrometer using
acetonitrile. Microanalysis was performed with Thermo Scientific
Flash 2000 elemental analyser. 2,2 -dithiodibenzoyl chloride was
prepared using a previously reported method [5]. Metal ion
extraction was performed based on the work of Cicek and it is
described in detail in the supporting information [20,26].
3
d
0
7.40 (t, 4H, J¼8.0 Hz), 7.70 (d, 4H, J¼8.0 Hz), 8.08 (d, 4H, J¼8.0 Hz).
13 1
C{ H} NMR (CDCl
3
,100 MHz)
d
28.6, 68.0,128.4,131.0,131.4,133.0,
þ
134.0, 134.4, 167.8. LC-MS m/z 816 (M , CH
3
CN, Error % ¼ 0). Anal.
Calc. for C36
32
H O
6
S
8
(MW¼817.16): C, 52.91; H, 3.95; S, 31.39%.
Found: C, 52.87; H, 3.92; S, 31.35%.
0
2.1. Synthesis of 2,2 -dithiodibenzoyl chloride
14,17,40,43-tetraoxa-2,3,11,20,28,29,37,46-octathiapentacyclo
2
22
3 3
[
46.4.0.0⁴,⁹.0 ⁷.0 ⁰, ⁵]dopentaconta
0
Classic Method: 2,2 -Dithiodibenzoic acid (1.0000 g, 3.26 mmol)
-1(48),4(9),5,7,22,24,26,30,32,34,49,51-dodecaene-10,21,36,47-
tetrone (U3). Prepared with triethylene glycol dithiol to the general
procedure-1 (2.0872 g, 11.45 mmol; 7 days) and general procedure-
2 (0.4612 g, 2.53 mmol, 1 h). Purification by column chromatog-
raphy (chloroform/ethyl acetate, 4:1, v/v) afforded a dark-yellow-
was added to a 100 mL round bottom flask. A slight excess of thi-
onyl chloride (1.5500 g, 13.05 mmol) was added into it, and the
mixture stirred for 16 h at reflux to afford a brown solid (68%).
0
Microwave-assisted Method: 2,2 -Dithiodibenzoic acid (1.0000 g,
3
.26 mmol) and thionyl chloride (1.6000 g, 13.50 mmol) was taken
brown oily product (2.8911 g, 28%; 1.3284 g, 58%, MW). FT-IR (g
ꢁ1
in a round bottom flask in StartSYNTH-Microwave Synthesis Lab-
cm ) 1700 (O]CeS stretch), 1253 (SeC(O)eC stretch), 1053 (CeS
ꢀ
1
station system.(MW, E¼1000 W, 80 C, 10 min, yield [68%). M.
stretch); H NMR (CDCl
3
, 400 MHz)
d
2.86 (t, 8H, J¼8.0 Hz), 3.72 (s,
ꢀ
ꢁ1
1
p.75e76 C; FT-IR (
g
cm ) 746, 786, 1109, 1160, 1242, 1350, 1450,
8H), 4.42 (t, 4H, J¼8.0 Hz), 7.20 (t, 4H, J¼8.0 Hz), 7,36 (t, 4H,
13
1
1560, 1600, 1725, 3080; HNMR (CDCl
3
, 100 MHz)
d
7.30e7.60 (m,
J¼8.0 Hz), 7.76 (d, 4H, J¼8.0 Hz), 8.04 (d, 4H, J¼8.0 Hz); C{ H}
4
H), 7.75 (d, 2H, J ¼ 8.0 Hz), 8.40 (d, 2H, J ¼ 8.0 Hz). LS-MS (m/z) 342
NMR (CDCl
3
, 100 MHz)
d
29.22, 69.60, 69.80, 125.60, 126.00, 128.00,
þ
þ
(
M ), 340, 338, 303, 233, 201, 179, 169, 167, 148, 133, 118, 102, 94.
130.40, 131.80, 132.60, 166.00. LC-MS m/z 904 (M , CH
3
CN, Error
%
¼ 0.0055). Anal. Calc. for C40
4.45; S, 28.34%. Found: C, 53.10; H, 4.49; S, 28.18%.
,3,11,14,22,23,31,34-octathiapentacyclo
H
40
O
8
S
8
(MW¼905.26): C, 53.07; H,
2.2. Synthesis of benzo-thio crown ethers, U1eU7
2
0
1
21
2 2
General procedure-1 (Classic). 2,2 -Dithiodibenzoyl chloride
[34.4.0.0⁴,⁹.0 ⁶, .0 ⁴, ⁹]tetraconta-
(
(
11.45 mmol), pyridine (22.90 mmol), and either a dithiol or diol
11.45 mmol) in the chloroform (150 mL) were added to a reaction
1(36),4(9),5,7,16,18,20,24,26,28,37,39-dodecaene-10,15,30,35-
tetrone (U4). Prepared with ethylene glycol to the general
procedure-1 (0.7099 g, 11.45 mmol; 72 h) and general procedure-2
(0.1569 g, 2.53 mmol, 1 h). Purification by column chromatography
(chloroform/ethyl acetate, 4:1, v/v) afforded a dark-yellow oily
flask. The reaction mixture was refluxed for 3e7 days under a ni-
trogen atmosphere, then left to cool to room temperature.
0
General procedure-2 (Microwave-assisted). 2,2 -dithiodibenzoyl
ꢁ1
chloride (2.53 mmol), pyridine (5.06 mmol), and either a dithiol or
diol (2.53 mmol) were taken in a round bottom flask, and chloro-
form (10 mL) was added. The reaction mixture was refluxed for 1 h
product (2.8911 g, 52%; 1.3960 g, 83%, MW). FT-IR (
(C]O stretch), 1247 (OeC(O)eC stretch), 1054 (CeO stretch);
NMR (CD OD, 400 MHz)
4.15 (s, 8H), 8.49 (d, 4H, J¼8.0 Hz), 8.80 (t,
g cm ) 1700
1
H
3
d