Synthesis and spectroscopic characterization of new double-armed benzo-15-crown-5 derivatives and their sodium complexes

Article abstract of DOI:10.1002/hc.21070

Double-armed crown ether aldehydes (1-3) were synthesized from the reaction of 2 equiv salicylaldehyde, 4-hydroxy-3-methoxybenzaldehyde (vanillin), and 3-hydroxy-4-methoxybenzaldehyde (iso-vanillin) with 4′,5′- bis(bromomethyl)benzo-15-crown-5. New crown

Full text of DOI:10.1002/hc.21070

Heteroatom Chemistry
Volume 24, Number 2, 2013
Synthesis and Spectroscopic Characterization
of New Double-Armed Benzo-15-Crown-5
Derivatives and Their Sodium Complexes
Onur Sahin and Zeliha Hayvalı
Department of Chemistry, Faculty of Science, Ankara University, 06100 Ankara, Turkey
Received 3 April 2012; revised 5 November 2012
in solution and in the crystalline state. The cation–
ABSTRACT: Double-armed crown ether aldehydes
polyether complexes are formed by ion–dipole inter-
action between the cation and the negatively charged
(1–3) were synthesized from the reaction of 2 equiv
salicylaldehyde,
4-hydroxy-3-methoxybenzaldehyde
oxygen symmetrically arranged in the polyether
ring. Selectivity for the alkali metal cation is dis-
played abundantly in biochemical systems such as
the sodium pump [3, 4]. Crown ethers also serve as
useful models for enzyme binding and can aid ion
transport across membranes [5–7]. They, owing to
ionophoric properties, resemble biologically impor-
tant ionophores such as the macrocyclic antibiotics
gramicidin, valinomycin, and nonactin, which are
known to make cell membranes selectively perme-
able to alkali metal cations [8]. Crown rings could en-
dow functional molecules with better performance
and new character, due to the hydrophobicity of the
outer ethylene groups and orderly arrangement of
the inner oxa atoms [9].
Benzo-condensed crown compounds having re-
active aldehyde substituent at the aromatic ring are
considered as an interesting starting material for the
synthesis of new molecules [10]. Crown ether con-
taining Schiff bases is known to bind cations in the
crown ether cavity in addition to the coordination
of a transition metal center through the imine group
[11–16].
(vanillin), and 3-hydroxy-4-methoxybenzaldehyde
(iso-vanillin) with 4ꢀ,5ꢀ-bis(bromomethyl)benzo-15-
crown-5. New crown ethers imine compounds (4–9)
were synthesized by the condensation of correspond-
ing crown ether aldehydes (1–3) with 4-amino-1,2-
dihydro-1,5-dimethyl-2-phenyl-3H-pyrazole-3-one and
2-furan-2-yl-methylamine. Sodium complexes (1a–
9a) of the crown compounds form crystalline 1:1
(Na+:ligand) stoichiometries and were also synthe-
sized. The structures of the crown ether aldehydes
(1–3), imine compounds (4–9), and complexes
(1a–9a) were confirmed on the basis of elemental
1
analyses, IR, H and 13C NMR, and mass spectrom-
ꢁC
etry.
2013 Wiley Periodicals, Inc. Heteroatom
Chem 24:100–109, 2013; View this article online at
wileyonlinelibrary.com. DOI 10.1002/hc.21070
INTRODUCTION
The cyclic polyethers described by Pedersen are of
special interest because of their remarkable com-
plexing properties [1, 2]. Crown ethers form com-
plexes with alkali and alkaline earth cations, both
These studies suggest that a suitable combina-
tion of a crown ether unit with other donor groups
may provide a possibility for preparing new func-
tionalized compounds.
In this paper, we have described the syntheses
and characterization of a series of novel double-
armed crown ether ligand and complexes, contain-
ing benzo-15-crown-5 moieties. We report (i) the
Correspondence to: Zeliha Hayvalı; e-mail: zhayvali@science
.ankara.edu.tr.
Contract grant sponsor: Scientific and Technical Research Coun-
cil of Turkey (TUBITAK).
Contract grant number: TBAG 109T034.
2013 Wiley Periodicals, Inc.
ꢁC
100

Synthesis and Spectroscopic Characterization of New Double-Armed Benzo-15-Crown-5 Derivatives 101
O
O
Br
O
O
O
O
O
HBr
Compond R1
R2
O
O
(HCHO)
2-OCH3 4-CHO
2-OCH3 5-CHO
1
2
3
n
O
Br
–
2-CHO
2
3
R1
1
OH
4
O
Br
Br
O
O
OCH3
O
O
O
R2
5
6
+
Na2CO3 /K2CO3
O
O
R2
O
O
O
CHO
O
R1
3
1–
FIGURE 1 Syntheses of dialdehydes (1–3).
H
C
R2
3
2
3
2
N
CHO
1
1
4
O
O
4
O
O
O
O
O
O
R1
R1
R1
R1
6
5
5
6
O
+
O
R
NH2
2
2
O
O
O
O
CHO
C
H
N
R2
1–3
4 9
–
Compound
R1
R2
4-HC=NR2 2-OCH3
5-HC=NR2 2-OCH3
4
5
6
O
2-HC=NR2
–
O
7
8
9
4-HC=NR2 2-OCH3
5-HC=NR2 2-OCH3
N
N
CH3
2-HC=NR2
–
H3C
FIGURE 2 Syntheses of Schiff bases (4–9).
syntheses of double-armed crown ether which have
dialdehyde (1–3) (Fig. 1), (ii) the syntheses and char-
acterization of new Schiff bases (4–9) (Fig. 2), (iii)
complexation with sodium in the crown ether cav-
ity (1a–9a) (Fig. 3), and (iv) analytical, physical, and
spectral (IR, 1H- and 13C-NMR, and MS) data.
NMR spectra were recorded on a Varian mercury,
high performance digital FT-NMR (400 MHz) spec-
trometer (SiMe4 as an internal standard) (USA).
Chemical shifts for proton and carbon resonances
were reported in ppm (δ). IR spectra were obtained
from a PerkinElmer spectrum 100 series spectrom-
eter (USA). Elemental analyses (C, H, N) were con-
ducted using the elemental analyzer LECO CHNS-
932; their results were found to be in good agreement
( 0.2%) with the calculated values (USA). Mass
spectrometric analyses were performed on the Wa-
ters 2695 Alliance ZQ LC/MS spectrometer (USA).
EXPERIMENTAL
Physical Measurements
Melting points were measured on a Thomas–Hoover
1
apparatus using a capillary tube (USA). H and 13C
Heteroatom Chemistry DOI 10.1002/hc

102 Sahin and Hayvalı
3
H
C
2
R1
4
R2
3
2
N
1
O
O
1
O
4
O
O
O
R2
O
5
6
Na+
R1
R1
O
O
O
6
5
Na+
R2
O
O
–
O
ClO4
O
R1
–
ClO4
C
H
N
R2
1a–3a
Compound R1
4a–9a
R2
Compound
R1
R2
2-OCH3 4-CHO
2-OCH3 5-CHO
4-HC=NR2 2-OCH3
5-HC=NR2 2-OCH3
(1a)
(2a)
(3a)
(4a)
(5a)
(6a)
O
-
2-CHO
2-HC=NR2
–
O
(7a)
(8a)
(9a)
4-HC=NR2 2-OCH3
5-HC=NR2 2-OCH3
N
N
CH3
2-HC=NR2
–
H3C
FIGURE 3 Proposed structures of sodium complexes (1a–9a).
tion of the starting material was observed by TLC
(silica, eluent; CHCl3). Then, water was added un-
til the solution turned cloudy. The white precipitate
formed was isolated and recrystallized from ethanol.
Specific details for compound 1 are given in Table 1.
Materials
All chemicals were of reagent grade. Accord-
ing to standard procedures, solvents were dried
and distilled before use. Tetraethylene glycol
dichloride [17], benzo-15-crown-5 [1], and 4ꢀ,5ꢀ-
bis(bromomethyl)benzo-15-crown-5
prepared according to the literature methods.
4-Hydroxy-3-methoxybenzaldehyde (vanillin), 3-
hydroxy-4-methoxybenzaldehyde
salicylaldehyde, 4-amino-1,2-dihydro-1,5-dimethyl-
2-phenyl-3H-pyrazole-3-one (4-aminophenazone,
4-aminoantipyrine; 4-AAP), and 2-furan-2-yl-
methylamine (furfuryamine) were purchased from
Aldrich (Dorset, UK) and used without further
purification. These solvents were dried and distilled
before use, according to the standard procedure.
Compound 3 was prepared by modification of the
reported procedure [19], and their spectroscopic
and analytical data are discussed below.
[18]
were
3,3ꢀ-[2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-
benzopentaoxacyclopentadecine-15,16-diylbis
(methyleneoxy)]bis(4-methoxybenzaldehyde) (2)
(iso-vanillin),
Compound 2 was prepared by following the pro-
cedure for compound 1 using a solution of 3-
hydroxy-4-methoxybenzaldehyde (0.67 g, 4.4 mmol)
and K2CO3 (0.60 g, 4.4 mmol). After recrystallization
from, EtOH, white crystals were obtained. Specific
details for compound 2 are given in Table 1.
2,2ꢀ-[2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-
benzopentaoxacyclopentadecine-15,16-diylbis
(methyleneoxy)]dibenzaldehyde (3)
Compound 3 was prepared by following the proce-
dure for compound 1 as mentioned above by taking
a solution of salicylaldehyde (0.54 g, 4.4 mmol). Af-
ter recrystallization from EtOH, white crystals were
obtained. Specific details for compound 2 are given
in Table 1.
4,4ꢀ-[2,3,5,6,8,9,11,12-Octahydro-1,4,7,10,13-
benzopentaoxacyclopentadecine-15,16-diylbis
(methyleneoxy)]bis(3-methoxybenzaldehyde) (1)
4-Hydroxy-3-methoxybenzaldehyde (0.67 g, 4.4
mmol) was dissolved in DMF (50 cm3). Na2CO3 (0.45
g, 4.4 mmol) was added in small amounts, and the
resulting reaction mixture was refluxed for 1 h. Sub-
sequently, 4ꢀ,5ꢀ-bis(bromomethyl)benzo-15-crown-5
(1.0 g, 2.2 mmol) in DMF (20 cm3) was added drop-
wise to the reaction mixture. The resulting solution
was refluxed for 10 h, then the complete consump-
General Methods for Preparing Schiff Bases
(4–9)
The corresponding amine (4-aminophenazone and
furfuryamine) (2.0 mmol) was dissolved in EtOH
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Spectroscopic Characterization of New Double-Armed Benzo-15-Crown-5 Derivatives 103
TABLE 1 Analytical Data and Experimental Details of the Compounds (1–9 and 1a–9a)
Elemental Analyses (%) Calc. (Found)
Compound
Formula
Color
Yield (%)
mp (◦C)
C
H
N
1
C32H36O11
C32H36O11
White
White
White
Yellow
Yellow
White
Yellow
Yellow
Yellow
White
Yellow
Yellow
White
Yellow
Yellow
White
White
Yellow
86
73
79
39
45
49
38
47
51
49
41
62
61
58
67
45
54
69
140
135
131
169
124
123
122
121
258
64.42 (64.45)
64.42 (64.61)
67.15 (67.35)
66.83 (66.49)
66.83 (66.85)
69.15 (69.33)
65.84 (65.81)
67.07 (67.14)
68.86 (68.84)
53.45 (53.31)
53.45 (53.04)
54.68 (54.74)
57.50 (57.22)
57.50 (57.35)
58.79 (58.59)
59.53 (59.67)
59.53 (59.20)
60.67 (60.62)
6.08 (5.96)
6.08 (6.15)
6.01 (6.23)
6.14 (6.01)
6.14 (6.09)
6.09 (6.26)
6.15 (6.03)
6.05 (6.07)
6.00 (6.03)
5.05 (5.07)
5.05 (4.90)
4.89 (4.85)
5.29 (5.28)
5.29 (5.26)
5.18 (5.16)
5.37 (5.52)
5.37 (5.28)
5.29 (5.37)
–
–
–
2
3
C32H36O11
4
C42H46N2O11
C42H46N2O11
3.71 (3.67)
3.71 (3.74)
4.03 (4.31)
8.53 (8.63)
8.69 (8.72)
9.27 (9.29)
–
5
6
C40H42N2O9
7
C54H58N6O11.H2O
C54H58N6O11
C52H54N6O9
C32H36O11 NaClO4
C32H36O11 NaClO4
8
9
1a
2a
3a
4a
5a
6a
7a
8a
9a
168–170
210
223
134–136*
229*
177
160
132
233*
–
–
C
30H32O9 NaClO4
C42H46N2O11 NaClO4
C42H46N2O11 NaClO4
C40H42N2O9 NaClO4
54H58N6O11. NaClO4
54H58N6O11 NaClO4
C52H54N6O9 NaClO4
3.19 (3.16)
3.19 (3.23)
3.43 (3.45)
7.71 (7.80)
7.71 (7.65)
8.16 (8.09)
C
C
*Decompose.
(20 mL). Double arm crown aldehyde (1–3) (1.0
mmol) was dissolved in EtOH and added dropwise.
The resulting solution was stirred under reflux for
3 h, and the reaction mixture was allowed to stand
for 2 h at room temperature. Yellow crystals formed,
and these were recrystallized from EtOH. Specific
details for each compound are given in Table 1.
and 79%, respectively. A direct reaction of 1 equiv
of aldehyde (1–3) with 1 equiv of appropriate amine
(furfurylamine or 4-aminoantipyrine) in ethanol
gives the corresponding new imine compounds (4–
9). The sodium complexes (1a–9a) were prepared
by treating a solution of appropriate aldehyde (1–9)
with NaClO4.
The structures of the ligands and sodium com-
plexes were verified by the elemental analysis, FT-IR,
1H and 13C NMR, and mass spectra. Analytical data
and experimental details of compounds (1–9 and 1a–
9a) are given in Table 1. Various attempts to obtain
single crystals of the ligands and complexes have so
far been unsuccessful.
General Methods for Preparing Sodium
Complexes (1a–9a)
The respective crown ether (1–9) (1.44 mmol) and
NaClO4 (0.17 g, 1.44 mmol) were dissolved in dry
EtOH (10 mL) and heated to reflux for 2 h. The pre-
cipitated complex was filtered and washed with di-
ethyl ether. Specific details for each sodium complex
are given in Table 1.
IR Spectra
Selected IR data of the crown ethers and alkali metal
complexes are shown in Table 2. In the infrared
spectra of crown ether, aldehydes (1–3) and their
sodium complexes (1a–3a) strong bands in the re-
RESULTS AND DISCUSSION
Synthesis
The synthetic procedure for the preparation of
the crown ether aldehydes (1–3) consists of two
steps. First, 4-hydroxy-3-methoxybenzaldehyde,
3-hydroxy-4-methoxybenzaldehyde, and salicylalde-
hyde were reacted with Na2CO3 or K2CO3 in DMF
to give the corresponding sodium alkoxide. Second,
the obtained sodium salts were converted to the
corresponding new crown ether aldehydes (1–3) by
gion 1676–1687 cm−1 can be assigned to the ν(C
O)
stretching. In the IR spectra of imine compounds
(4–9) and their sodium complexes (4a–9a), no bands
due to ν(C
could be observed, indicating the con-
O)
densation of the aldehyde groups. The character-
istic imine (νC N) stretching bands attributable to
the azomethine group (HC N) were observed 1637,
1636, 1633, 1647, 1638, and 1651 cm−1 (for 4–9)
and 1638, 1638, 1639, 1639, 1648, and 1657 cm−1
(for 4a–9a), respectively. The intense bands at 1600–
1489 cm−1 correspond to the stretching vibrations
reacting
with
4ꢀ,5ꢀ-bis(bromomethyl)benzo-15-
crown-5. Crown ether aldehydes (1–3) successfully
synthesized with yields in the range of 86%, 73%,
Heteroatom Chemistry DOI 10.1002/hc

104 Sahin and Hayvalı
TABLE 2 Selected IR Bands of the Compounds (1–9 and 1a–9a)
Compound
ν(C
ν(C
ν(C
ν(C
ν(C
ν(C
ν(Cl
ν(O
Cl O)
O)
H aliph.)
N)
C)
O
C arom.)
O
C aliph.)
O)
1
1678 (s) 2928–2875 (m)
1686 (s) 2934–2865 (m)
1678 (s) 2911–2862 (m)
–
–
–
1584–1514 (s) 1287–1268 (s) 1134–1032 (s)
1584–1513 (s) 1266–1237 (s) 1130–1023 (s)
1599–1523 (s) 1283–1230 (s) 1120–1032 (s)
–
–
2
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
–
3
4
–
2931–2869 (m) 1637 (s) 1581–1507 (m) 1263–1223 (s) 1135–1031 (s)
2921–2865 (w) 1636 (m) 1583–1517 (s) 1264–1238 (s) 1132–1021 (s)
2940–2885 (m) 1633 (m) 1598–1523 (m) 1298–1223 (s) 1134–1048 (s)
2919–2870 (m) 1647 (s) 1594–1509 (s) 1258–1228 (s) 1122–1032 (s)
2920–2867 (m) 1638 (m) 1596–1509 (s) 1259–1228 (s) 1131–1024 (s)
2945–2877 (w) 1651 (s) 1591–1510 (s) 1241–1198 (s) 1132–1047 (s)
5
–
–
–
–
6
7
8
9
–
1a
2a
3aa
4aa
5a
6aa
7aa
8a
9aa
1676 (s) 2927–2878 (w)
1681 (s) 2941–2885 (w)
1687 (s) 2924–2877 (m)
–
–
–
1596–1514 (s) 1267–1241 (s) 1133–1032 (s) 1092 (s)
1584–1512 (s) 1267–1235 (s) 1122–1042 (s) 1097 (s)
1600–1516 (s) 1288–1243 (s) 1097–1032 (s) 1097 (s)
655 (s)
655 (s)
655 (s)
653 (s)
656 (s)
658 (s)
623 (s)
623 (s)
621 (s)
–
–
–
–
–
–
2934–2875 (m) 1638 (m) 1583–1507 (s) 1264–1229 (s) 1110–1029 (s) 1110 (s)
2924–2875 (m) 1638 (m) 1584–1508 (s) 1260–1231 (s) 1120–1011 (s) 1093 (s)
2941–2879 (m) 1639 (m) 1598–1515 (m) 1290–1245 (s) 1098–1041 (s) 1098 (s)
2937–2877 (m) 1639 (s) 1594–1509 (s) 1261–1226 (s) 1092–1031 (m) 1092 (s)
2909–2876 (w) 1648 (s) 1596–1513 (s)
2919–2876 (m) 1657 (s) 1594–1489 (s) 1235–1203 (s) 1108–1054 (m) 1108 (s)
1257 (s)
1130–1020 (m) 1102 (s)
w: Weak; m: medium; s: strong;
aνCl
peaks overlapping with ν(C
.
C aliph.)
O
O
of the benzene rings (νC C) of the compounds. The
10.02 ppm (for 4a–9a). Considering the N CH
proton chemical shifts for the Schiff bases (4–6 and
7–9), we note a shielding of 1.44 ppm on passing
from furfurylamine to 4-aminophenazone of the cor-
responding Schiff bases, respectively. The observa-
tions of furfurylamine N CH2 protons at 4.76 ppm
(for 4), 4.71 ppm (for 5), and 4.70 ppm (for 6) in-
dicate the imine compounds. For compounds 7–9,
the observation of CCH3 and NCH3 protons at
2.50, 2.40, and 2.25 ppm ( CCH3) and 3.15, 3.10,
3.14 ppm ( NCH3) indicate the imine compounds.
The aliphatic protons ( OCH2 ) were seen as a
singlet at 5.13–5.32 ppm. 1H NMR spectra of all
the compounds show the aromatic protons as mul-
tiplet peaks between 6.22 and 7.99 ppm, whereas
the crown ether protons ( OCH2CH2O ) appear as
multiplet peaks between 3.29 and 4.29 ppm.
aromatic and aliphatic νC
stretching vibration
O
C
bands are observed at 1298; 1198 cm−1 and 1134;
1011 cm−1 for the ligands and complexes. The IR
spectra of the ligands (1–9) and complexes (1a–9a)
were almost of the s−ame frequency.
The anion ClO4 in sodium complexes (1a–9a)
give rise to IR absorption bands at 1092, 1097,
1097, 1110, 1093, 1098, 1092, 1102, and 1108 cm−1
and 655, 655, 655, 653, 656, 658, 623, 623, and
621 cm−1. These bands attributable to the asymmet-
ric νas(Cl O) stretching modes ca. between 1092 and
1110 cm−1 and the asymmetric νas(O Cl O) bend-
ing modes ca. between 621 and 658 cm−1, suggesting
that both bounded and uncoordinated free anions
are present.
1
The H NMR spectra of the sodium complexes
1H and 13C NMR Spectroscopy
are approximately the same as in the correspond-
ing ligand spectra, but the 1H NMR spectra provide
compelling evidence for the ligand and their sodium
complexes. Thus, different multiplet peaks shape
1
In the H and 13C NMR spectra, the integral ratio
of the aliphatic and aromatic protons for all com-
pounds (1–9 and 1a–9a) indicates symmetry in the
1
molecules. The H NMR spectral data are summa-
was seen at crown ether protons ( OCH2CH2O
)
rized in Table 3. The 1H NMR spectra of the aldehy-
des (1 and 2), imine compounds (4, 5, 7, and 8),
and complexes (4a, 5a, 7a, and 8a) show singlet
peaks at the crown ether protons region correspond-
ing to OCH3 protons. The singlet peaks at 9.85,
9.83, and 10.42 ppm belonging to aldehyde protons
region (between 3.29 and 4.29 ppm) of the ligand
and each sodium complexes [19] (Fig. 4). Although
three multiplet peaks were seen for the ligands (1,
6, and 8), four peaks were observed for the sodium
complexes (1a, 6a, and 8a) at the crown ether proton
peaks region.
The 13C NMR spectral data for compounds (1–
5, 7, 9) are summarized in Table 4. The aldehyde
carbons ( CHO) of compounds 1–3 were observed
at 191.82, 191.75, and 189.39 ppm. The azomethine
(
CHO) (for 1–3) disappear after the condensation
reactions. The azomethine protons were observed as
a singlet peak at 8.25, 8.19, 8.76, 9.69, 9.63, and 10.21
ppm (for 4–9) and 8.23, 8.30, 8.76, 9.67, 9.58, and
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Spectroscopic Characterization of New Double-Armed Benzo-15-Crown-5 Derivatives 105
COH
CH
N
AHr
2
OHC
2
NHC
O
2
CH
2
OHC
3
OHC
3
NHC
c
3
d
CH
b
C
a
Heteroatom Chemistry DOI 10.1002/hc

106 Sahin and Hayvalı
Ligand
Na+ Complex
1
1a
H3CO
O
b
c
a
CHO
CHO
O
O
d
O
O
O
O
H3CO
1
6
6a
b
a
c
N
N
O
O
O
O
d
O
O
O
O
O
6
8
8a
CH3
H3
C
N
H3CO
N
b
a
c
N
O
O
O
d
O
O
O
O
O
O
N
N
H3CO
N
H3
C
CH3
8
1
FIGURE 4 1H NMR spectra of the crown ether protons (–OCH2CH2O–) for the ligands and complexes (1, 1a, 6 6a, 8, and 8a).
carbons were detected at 162.62, 162.48, 157.11, and
158.20 ppm for compounds 4, 5, 7, and 9, respec-
tively. In the 13C NMR spectra, four crown ether
carbons ( OCH2CH2O ), aliphatic and aromatic
carbons were detected in the expected region and
expected number.
ric. The spectra confirm the identities of the com-
plexes; all signals were found in the expected shift
range with correct intensities in the 13C NMR spec-
tra. The chemical shift change was due to the inter-
action of the crown ether ring with sodium cation,
which indicates that a new complex was formed.
But slight downfield or upfield shifts in the 13C
NMR signals were observed for the complexes. When
ligand and sodium 13C NMR spectrum are com-
pared, small but not significant changes are seen in
crown ether OCH2CH2O peaks as referenced by
The 13C NMR spectral data for sodium com-
plexes (1a–9a) are summarized in Table 5. In
the 13C NMR spectra, four crown ether carbon
(
OCH2CH2O ) peaks, aliphatic and aromatic car-
bons indicate that the molecules 1a–9a are symmet-
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Spectroscopic Characterization of New Double-Armed Benzo-15-Crown-5 Derivatives 107
CHO
O
C
CH
N
Ar-C
O
2
CH
2
OCH
-
2
OCH
2
NCH
3
OCH
3
NCH
3
CH
d
a
a
a
a
b
b
b
C
a
b
Heteroatom Chemistry DOI 10.1002/hc

108 Sahin and Hayvalı
CHO
O
C
CH
N
Ar-C
O
2
CH
2
OCH
2
OCH
2
NCH
3
OCH
3
NCH
3
CH
d
a
a
a
a
b
b
b
b
b
C
a
b
Heteroatom Chemistry DOI 10.1002/hc

Synthesis and Spectroscopic Characterization of New Double-Armed Benzo-15-Crown-5 Derivatives 109
several previous works [11, 20–25]. It is well known
[C11H11N2O – H] groups, respectively. All of the mass
spectra show that this fragmentation pattern pro-
ceeding by the loss of etheric chains is in accordance
with the literature [26–28]. The molecular ion peaks
and fragments of the ligands and complexes support
the proposed structures.
that the Na+ cations, on the other hand, are suf-
ficiently small to fit into the cavities of benzo-15-
crown-5 moieties of the crown ethers [23–25]. Ac-
cording to the literature, the complexation of the
ligands with Na+ cations can be called as “filling
complexes.” In conventional “filling complexes,” low
chemical shifts are especially observed for the aro-
matic and crown ether protons. In the spectrum of
the complexes (1a–9a), signals of the crown car-
bon atoms are slightly shifted toward lower ppm
values. This behavior is typical of inclusion com-
plexes where Na+ ion is linked to oxygen atoms
in the benzo-15-crown-5 via ion-dipole interactions.
Apparently, Na+ ion matches the cavity of benzo-
15-crown-5 in the complex well and thus is just ac-
commodated in the crown ether ring to form 1:1
cation:ligand complexes [19]. In all of complex (1a–
9a), the characteristic crown ether OCH2CH2O
carbons were observed at between 67.46 and 70.99
ppm, as expected. The signals of the aromatic car-
bons were detected in the expected region and were
equal to the number in the proposed structures of
compounds 1a–9a. Aliphatic OCH3 carbons of the
compounds (1a, 2a, 4a, 5a 7a, and 8a) were de-
tected at 56.13, 55.24, 56.18, 55.98, 55.86, and 55.55
ppm, respectively. The aldehyde carbons ( CHO) of
compounds (1a–3a) were observed at 191.13, 191.14,
and 189.58 ppm, respectively. As expected, the imine
carbons (HC N) of the compounds (4a–9a) were ob-
served at 162.83, 162.76, 158.24, 157.23, 159.71, and
158.43 ppm, respectively. C O carbons of the com-
pounds (7a–9a) were detected at 161.18, 162.12, and
161.29 ppm, respectively.
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The APCI and API-ES mass spectra of compounds
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with the suggested structures. The mass spectrum
of compound 1 was obtained by the APCI technique,
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Heteroatom Chemistry DOI 10.1002/hc