Novel benzo-15-crown-5/C60 dyads with different chains: Synthesis and complexation properties

Article abstract of DOI:10.2174/157017861101140113155347

Using benzo-15-crown-5 derivatives as starting materials, two novel benzo-15-crown-5/C₆₀ dyads with different linking chains were designed and synthesized in good yields by 1,3-dipolar cycloaddition of azomethine ylide generated in situ from al

Full text of DOI:10.2174/157017861101140113155347

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2
Letters in Organic Chemistry, 2014, 11, 2-5
Novel Benzo-15-crown-5/C60 Dyads with Different Chains: Synthesis and
Complexation Properties
Biqiong Hong1,2, Fafu Yang1,3*, Jinqi Ye1, Hongyu Guo1 and Xiaoyun Yan4
2
1College of Chemistry and Chemical Engineering, Fujian Normal University, Fuzhou 350007, P.R. China; Command
Academy of Fuzhou, The Chinese People’s Armed Police Force, Fuzhou 350002, P.R. China; 3Fujian Key Laboratory of
Polymer Materials, Fuzhou 350007, P.R. China; 4College of Chemistry and Chemical Engineering, Xiamen University,
Xiamen, 361005, P.R. China
Received July 04, 2013: Revised September 09, 2013: Accepted September 12, 2013
Abstract: Using benzo-15-crown-5 derivatives as starting materials, two novel benzo-15-crown-5/C60 dyads with differ-
ent linking chains were designed and synthesized in good yields by 1,3-dipolar cycloaddition of azomethine ylide gener-
ated in situ from aldehyde and sarcosine tied to C60. It was found that their UV-Vis absorption spectra could be regulated
hypsochromically by metal ions complexation. The long and soft linking chain was favorable for cooperate interaction of
crown ether unit and C60 unit.
Keywords: C60, benzo-15-crown-5, chain, synthesis, complexation.
1. INTRODUCTION
different linking chains between C60 and crown ether on
properties were not studied up to now. In this paper, we wish
to report the design and synthesis of novel benzo-15-crown-
5/C60 dyads with different linking chains by 1,3-dipolar cy-
cloaddition. Also, it was found that the different linking
chain of benzo-15-crown-5/C60 dyads made different influ-
ences on their properties.
Fullerene has received considerable attention and much
research interest due to its remarkable photophysical, elec-
trochemical and chemical properties [1-3]. Many functional
groups or functional units have been introduced for tuning
the physical properties of C60 and for constructing su-
pramolecular architectures [4-7]. Among all kinds of C60
derivatives, [60]fullerene/crown ether conjugates represent
the most widely studied example of fullerenes integrating an
ether moiety. The covalent linkage of a crown ether moiety
on the fullerene core is a unique approach to the construction
of functional supramolecular fullerene assemblies [8], such
as fullerene crown ether with ꢀ-extended TTF derivative [9],
[60]fullerene/crown ether with photochemical addition [10],
C60/crown ether with Bingel reaction of malonates [11-13].
These target molecules have potential application to form
supramolecular complexes and assemblies by metal ion rec-
ognition. It was expected that cation binding would affect the
redox potential of the fullerene sphere, thereby providing an
electrochemically detectable sensoric signal for the recogni-
tion event, etc.
2. RESULTS AND DISCUSSION
The synthetic route was shown in (Scheme 1). 1, 3-
dipolar cycloaddition was a typical reaction for preparing C60
derivatives [5]. In order to accomplish 1, 3-dipolar cycload-
dition, the formylphenyl Benzo-15-crown-5 derivatives 2
and 6 with different linking chains were prepared preliminar-
ily in ideal yields. By reacting 2,3-dihydroxybenzaldehyde
with tetraethylene glycol disulfonate 1 using Na+ as template
cation, formylphenyl benzo-15-crown-5 derivative 2 was
obtained in 70% yield in “1+1” condensation mode. On the
other hand, the formylphenyl benzo-15-crown-5 derivative 6
was prepared by using benzo-15-crown-5 as starting material,
followed by nitration, reduction, acylation, and etherification
with 4-hydroxy benzaldehyde. Although, in the muti-step
synthetic procedures for compound 6, the purification was
simple with recrystallization and the yield was ideal in each
step. Subsequently, by treating compounds 2 or 6 with sarco-
sine and C60 in refluxing toluene, the novel benzo-15-crown-
5/C60 dyads 7 and 8 were obtained via 1,3-dipolar cycloaddi-
tion of azomethine ylides tied to C60. The isolated yields
were 33% and 38% after column chromatography, respec-
tively. Due to the crown ether/C60 dyads 7 and 8 with differ-
ent linking chains, it is expected they showed not only the
cooperation complexation action of C60 unit and crown ether
unit for guest, but also the influence of different linking
chains on the complexation ability, which was not discussed
in the literatures before.
Based on the above literatures of fullerene/crown ether
dyads, it could be concluded the properties of fullerene/
crown ether were decided on not only the structures of crown
ether ring but also the structures of linking chains between
fullerene and crown ether. 1,3-dipolar cycloaddition of
azomethine ylide was widely used to prepare fullerene de-
rivatives effectively, but it was seldom applied to synthesize
fullerene/crown ether [14]. Moreover, the influences of the
*Addresses correspondence to this author at the College of Chemistry and
Chemical Engineering, Fujian Normal University, Fuzhou 350007, P.R.
China and Fujian Key Laboratory of Polymer Materials, Fuzhou 350007,
P.R. China; Tel: 0086-591-83465225; Fax: 0086-591-83465225;
E-mail: yangfafu@fjnu.edu.cn
1875-6255/14 $58.00+.00
© 2014 Bentham Science Publishers

Novel Benzo-15-crown-5/C60 Dyads with Different Chains
Letters in Organic Chemistry, 2014, Vol. 11, No. 1 3
TsCl
OTs
O
O
TsO
O
O
O
O
HO
OH
1
CHO
OHC
OH
OH
O
O
1
O
O
MeCN, Na2CO3
O
2
NO2
O
O
NH2
O
O
O
O
O
O
O
HNO3, HOAc
O
N2H4, Pt
O
O
O
O
O
O
3
4
Cl
Cl
O
O
OHC
OH
O
CHO
NH
O
Cl
NH
O
O
O
O
O
O
O
K2CO3
6
O
O
5
CH3
N
CH3
O
O
N
O
O
O
O
O
HN
6
2
O
O
O
sarcosine
O
sarcosine
O
8
7
Scheme 1.
The structures of new compounds 7 and 8 were charac-
the oxygen atoms of crown ether moieties, which could regu-
late the absorption spectra of crowned [60]fullerpyrrolidine.
Moreover, the absorbance of compound 8 after complexation
increased obviously comparing with the change of com-
pound 7. These results indicated that compound 8 with long
and soft linking chain produced stronger cooperation com-
plexation than that of compound 7 with short and rigid link-
ing chain. These phenomena were not reported before, which
might be attributed to the soft chain of compound 8 which
was favorable for the crown ether unit closing to fullerene
and then producing stronger interaction between them.
1
terized by elemental analyses, UV, IR, ESI-MS, H NMR
spectra, etc. The UV spectra of compounds 7 and 8 were
shown in (Figs. 1 and 2). The typical absorption features of
mono-fulleropyrrolidine at 432 nm could be seen. Their ESI-
MS spectra showed corresponding molecular ion peaks at
1043.66 and 1193.68. Also, all the protons of their 1H NMR
spectra were assigned well. Especially, the typical split of
NCH2 (a and a’) on pyrrole rings were observed clearly. All
these typical characterizations of spectra were similar to the
structures of mono-fulleropyrrolidine in the literature [15].
In order to test the influence of different linking chains
on their property, UV-Vis absorption spectra of compounds
7 and 8 in CHCl3-MeCN (1:1, v/v) with addition of Na+ were
measured at room temperature as shown in (Figs. 3 and 4). It
could be seen that the absorption of compounds 7 and 8 was
hypsochromically shifted by metal ions complexation. When
Na+ was added, the peaks of absorption of compounds 7 and
8 shifted from 328 nm and 276 nm to 325 nm and 270 nm,
respectively. The hypsochromic effect was attributed to the
complexation with a cation reducing the donor character of
In a word, two novel benzo-15-crown-5/C60 dyads with
different linking chains were designed and synthesized in
good yields by 1,3-dipolar cycloaddition. Their UV-Vis ab-
sorption spectra could be regulated hypsochromically by
metal ion complexation. The long and soft linking chain was
favorable for cooperate interaction between crown ether unit
and C60 unit. The in-depth studies on syntheses and proper-
ties of these kinds of dyads with other linking chains will be
investigated in the following work.

4
Letters in Organic Chemistry, 2014, Vol. 11, No. 1
Hong et al.
Fig. (3). UV-Vis absorption spectra of compound 7 with addition of
anhydrous sodium perchlorate, ratio of 7/salt = 1:20, concentration
of 7: in 2.0ꢀ10-5M, solvent: CHCl3-MeCN (1:1, v/v).
Fig. (1). UV-vis absorption spectrum of compound 7.
Fig. (4). UV-Vis absorption spectra of compound 8 with addition of
anhydrous sodium perchlorate, ratio of 8/salt = 1:20, concentration
of 8: 2.0ꢀ10-5M, solvent: CHCl3-MeCN (1:1, v/v).
formed at Vario EL III Elemental Analyzer. Compounds 2
and 4 were prepared according to the literature [16].
Fig. (2). UV-vis absorption spectrum of compound 8.
3.2. The Procedure for Synthesis of Compound 6
Compound 4 (1.0 g, 3.5 mmol) and 2-chloroacetyl chlo-
ride (0.4 g, 3.6 mmol) were stirred in 20 mL dry CH2Cl2 at
room temperature for overnight purged with N2. After reac-
tion, the solvent was evaporated to dryness and the light yel-
low solid was afforded. Then 4-hydroxybenzaldehyde (0.44
g, 3.6 mmol), K2CO3 (0.69 g, 5 mmol) and 50 mL of MeCN
were added and refluxed for 12 h. TLC detection showed the
disappearance of materials. After cooling, the solution was
filtered and the solvent was evaporated to dryness. Then 20
mL of methanol was added and precipitation was formed.
After dryness, compound 6 was obtained as gray white solid
3. EXPERIMENTAL
3.1. Apparatus and Materials
All reagents were purchased from commercial suppliers
and used without further purification. All the solvents were
purified according to the standard methods before use. H
NMR spectra were recorded in CDCl3 on a Bruker-ARX 400
instrument at 30oC. IR spectra were recorded on a Thermo
Nicollet AVATAR 5700 FTIR spectrometer using KBr pel-
let. The UV-vis absorption spectra were measured on a com-
puter-controlled Shimadzu UV2501-PC spectrophotometer.
ESI-MS spectra were obtained from DECAX-30000 LCQ
Deca XP mass spectrometer. Elemental analyses were per-
1
1
in yield of 80%. Compound 6: H NMR (400 MHz, CDCl3)
ꢁ: (ppm) 3.82~4.15(m, 16H, OCH2CH2O), 4.96 (s, 2H,

Novel Benzo-15-crown-5/C60 Dyads with Different Chains
Letters in Organic Chemistry, 2014, Vol. 11, No. 1 5
OCH2CO), 6.72~7.45 (m, 7H, ArH), 7.96 (s, 1H, CH), 8.89
(s, 1H, NH).
ogy in Fujian Province University and Program for Excellent
young researchers in University of Fujian Province
(JA10056) were greatly acknowledged.
3.3. The Procedure for Synthesis of Compound 7
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CONFLICT OF INTEREST
The authors confirm that this article content has no
conflict of interest.
ACKNOWLEDGEMENTS
[15]
[16]
Financial support from the National Natural Science
Foundation of China (No: 20402002), Fujian Natural Sci-
ence Foundation of China (No. 2011J01031), Project of Fu-
jian provincial department of education(JA11044), the Pro-
gram for Innovative Research Team in Science and Technol-