Synthesis of a functionalised calix[4]arene and its interactions with hemicucurbit[6,7]urils and cucurbit[8]uril

Article abstract of DOI:10.1016/j.tet.2018.06.020

In the present work, we synthesised a functionalised calix[4]arene with 5,11-di(N-methyl-E-(4-pyridylethylene) moiety (CX[4]), and investigated interactions of it with HemiMeQ[6], HemiMeQ[7], and Q[8]) in both water and DMSO using fluorescence spectrophotometry and ¹H NMR spectroscopy. Titration ¹H NMR spectra revealed that Q[n]s prefers to include the N-methyl-E-(4-pyridylethylene) moiety. In particular, the interaction of CX[4] with Q[8] in water resulted in intense fluorescence emission, and this interaction system can respond to compounds such as amantadine.

Full text of DOI:10.1016/j.tet.2018.06.020

Accepted Manuscript
Synthesis of a functionalised calix[4]arene and its interactions with
hemicucurbit[6,7]urils and cucurbit[8]uril
Jin Ming Zhu, Li Xia Chen, Kai Chen, Xi Zeng, Zhu Tao
PII:
S0040-4020(18)30691-4
10.1016/j.tet.2018.06.020
TET 29616
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 3 May 2018
Revised Date: 4 June 2018
Accepted Date: 8 June 2018
Please cite this article as: Zhu JM, Chen LX, Chen K, Zeng X, Tao Z, Synthesis of a functionalised
calix[4]arene and its interactions with hemicucurbit[6,7]urils and cucurbit[8]uril, Tetrahedron (2018), doi:
10.1016/j.tet.2018.06.020.
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ACCEPTED MANUSCRIPT

ACCEPTED MANUSCRIPT
Synthesis of a functionalised calix[4]arene and its interactions with
hemicucurbit[6,7]urils and cucurbit[8]uril
Jin Ming Zhu a, Li Xia Chen a, Kai Chen*b, Xi Zeng*a, Zhu Tao*a
a Key Laboratory of Macrocyclic and Supramolecular Chemistry of Guizhou Province, Guizhou University, Guiyang 550025, China. Email:gzutao@263.net(Z.
Tao); zengxi1962@163.com(X. Zeng)
b Collaborative Innovation Center of Atmospheric Environment and Equipment Technology, Jiangsu Key Laboratory of Atmospheric Environment Monitoring
and Pollution Control, School of Environmental Science and Engineering, Nanjing University of Information Science & Technology, Nanjing 210044, China.
Email:kaichen85@nuist.edu.cn or catqchen@163.com(K. Chen)
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
In the present work, we synthesised a functionalised calix[4]arene with
5,11-di(N-methyl-E-(4-pyridylethylene) moiety (CX[4]), and investigated
interactions of it with HemiMeQ[6], HemiMeQ[7], and Q[8]) in both water and
1
DMSO using fluorescence spectrophotometry and H NMR spectroscopy. Titration
Available online
1H
NMR
spectra
revealed
that Q[n]s prefers
to
include
the
N-methyl-E-(4-pyridylethylene) moiety. In particular, the interaction of CX[4] with
Q[8] in water resulted in intense fluorescence emission, and this interaction system
can respond to compounds such as amantadine.
Keywords:
functionalized calix[4]arene
hemimethyl-substituted cucurbit[n]urils
molecular interactions
2018 Elsevier Ltd. All rights reserved
.
supramolecular assemblies
interaction.33 Kögerler and co-workers first demonstrated some
Q[n]/POM-based hybrid compounds, which have characteristic
large channels constructed from Q[n] molecules and POM
anions, through the outer surface interaction of
cucurbit[n]urils.37 Lin and co-workers first demonstrated two
1. Introduction
Supramolecular chemistry was largely established through
novel works by Lehn, Cram, Pedersen, and their co-workers,
who explored host-guest chemistry through noncovalent
interactions of some typical hosts such as crown ethers,
calixarenes, and cyclodextrins with various guests.1-3
Cucurbit[n]urils (Q[n]s) obtained by condensing glycolurils and
formaldehyde in concentrated HCl 4–8 are a type of relevant new
host originally derived from Q[6] as described by Mock in
1981.4,5 Q[n]s are characterised by a rigid hydrophobic cavity
and two polar portals rimmed with carbonyl groups, and they
serve as ideal building blocks for the construction of various
supramolecular assemblies through host-guest interactions.9–14
Research from ourselves and others revealed that the positive
electro-potential outer surface of Q[n] can also give rise to a
variety of Q[n]-based supramolecular assemblies.15–21
Calix[n]arenes were obtained from reactions between phenols
and aldehydes by Adolph von Baeyer in 1872,22–24 and more
derivatives were assigned by Zinke and Zieglerin 1944,25,26 and
were eventually termed calixarenes by Gutsche in 1978.27
Calix[n]arenes are also characterised by a hydrophobic cavity
constructed of phenyl rings bridged by methylene groups.
Importantly, multiple reactive sites on the phenyl rings allow
easily functionalisation of calix[n]arenes.28–30 With the
development of supramolecular chemistry, more and more
supramolecular assemblies involved with multi-macrocyclic
hosts or building blocks, which exhibited novel properties
which are different from those of the original macrocyclic hosts,
respectively.31-38 For example, Liu and co-workers demonstrated
the difference between rotaxane and pseudorotaxane with two
hosts, α-CD, Q[7], and an axle guest bearing two terminal
ferrocene groups.31 Using a naphthol-modified β-cyclodextrin,
they successfully constructed a novel supramolecular ternary
polymer mediated by Q[8] based on the charge-transfer
supramolecular
architectures
assembled
from
the
supermolecular building blocks of calixarenes and cucurbiturils,
which exhibited the outer surface interaction of cucurbit[n]urils
in directing the supramolecular assemblies.38 Thus,
supramolecular interactions between cucurbit[n]urils and other
macrocyclic host, such calix[n]arenas occur not only through
outer surface interactions of cucurbit[n]urils,21 but also through
host-guest
interactions
between
cucurbit[n]urils
and
functionalised species.
In the present work, we synthesised a functionalised
calix[4]arene with 5,11-di(N-methyl-E-(4-pyridylethylene))
moieties, which could serve as guests able to interact with
different Q[n]s (hereafter referred to as CX[4]; Fig. 1a). This
functionalised calix[4]arene is almost insoluble in aqueous
solution but dissolves readily in DMSO. In order to investigate
the interactions of this CX[4] with cucurbit[n]urils, we selected
two hemimethyl-substituted cucurbit[n]urils (HemiMeQ[n]s),39
HemiMeQ[6] and HemiMeQ[7], that dissolve in both aqueous
solution and DMSO, and a larger normal regular cucurbit[n]uril,
Q[8] (Fig. 1b−d). Interactions of this CX[4] with the three
selected Q[n]s revealed that the N-methyl-E-(4-pyridylethylene)
Fig. 1. Structures of (a) the functionalised calix[4]arene; (b) HemiMeQ[6];
(c) HemiMeQ[7]; (d) Q[8].
1

moiety of CX[4] can be included in the cavity of HemiMeQ[n]s.
ACCEPTED MANUSCRIPT
Although we did not directly observe the interaction of CX[4]
with Q[8] due to the poor solubility of both components in
aqueous solution, the intense fluorescence emission indicated
strong interaction, and more importantly, the CX[4]-Q[8]
interaction system could respond to organic compounds such as
amantadines.
2. Results and Discussion
2.1. Design and synthesis of the functionalised calix[4]arene
(CX[4])
Previous work showed that 4-sulfocalix[4]arene or
4-sulfocalix[6]arene (SC[n]As) can interact with Q[6] and form
SC[n]As/Q[6]-based supramolecular assemblies.38 Similarly, we
recently demonstrated a supramolecular assembly constructed
of 4-sulfocalix[4]arene and Q[7].40 The driving force for the
formation of these supramolecular assemblies is attributed to
the outer surface interactions of cucurbit[n]urils via the positive
electro-potential outer surface of cucurbit[n]urils.21 Interestingly,
multiple reactive sites on the phenyl rings on C[n]As can be
used to introduce a variety of typical guest moieties, resulting in
host-guest interactions of Q[n]s with functionalised
calix[n]arenes. Thus, after a series of reactions, we eventually
obtained
a new pyridyl-modified calix[4]arene, namely
5,11-di(N-methyl-(4-pyridylethylene))-25,27-bis(3-bromopropo
xy)-26,28-dihydroxy-calix[4]arene (CX[4]). Details of its
synthesis are included in Supplementary Fig. S1-.S5. Analysis
by ESI-MS supported the structure of CX[4], with molecular
ions such as m/z = 1157.57 [CX[4] + H+], consistent with the
parent CX[4] coordinating to H+ ions (Supplementary Fig. S6).
Although pyridyl moieties were introduced into calix[4]arene,
the water solubility of the modified calix[4]arene was not
obviously improved. Therefore, we utilised the polar solvent
DMSO in which the modified calix[4]arene, HemiMeQ[6], and
HemiMeQ[7] could be dissolved.
2.2. Interaction of CX[4] with selected Q[n]s
Given the solubility of CX[4], which is easily dissolved in
DMSO but almost insoluble in water, interactions of CX[4]
with Q[n]s were mainly explored in DMSO, and interactions of
CX[4] with Q[8] were investigated in water, because Q[8] is
insoluble in DMSO.
Fig. 2. Titration 1H NMR spectra (500 MHz, DMSOd6) of HemiMeQ[6] in
the presence of 0 (a), 0.25 (b), 0.50 (c), 0.75 (d), and 1.00 (e) equivalents of
CX[4], and (f) 1H NMR spectrum of neat CX[4] at 25°C.
2.2.1. Interaction of CX[4] with HemiMeQ[6] and
HemiMeQ[7]in DMSO
In general, the pyridyl moiety and its derivatives can be
encapsulated inside the cavity of Q[n]s (n >6) and can therefore
reveal interactions between HemiMeQ[n]s and CX[4]. It is
clearly evident from Fig. 2 that only one set of proton signals
for CX[4] was observed with increasing number of equivalents
of CX[4] (Fig. 2a−e), suggesting that these are averaged signals
of free and bound CX[4] molecules due to a rapid exchange rate
between binding and release of CX[4] on the NMR timescale.
The resonances of pyridyl and methyl moieties on CX[4] lie in
different magnetic environments, the pyridyl proton resonances
(Hm) are shifted downfield, while the methyl proton resonances
(Hn) are shifted upfield. This indicates that only the methyl
group of CX[4] is contained within the cavity of HemiMeQ[6],
while the other part of CX[4] remains outside the cavity.
moiety of CX[4] appeared to experience an upfield shift,
suggesting that HemiMeQ[7] can include the whole
N-methyl-(4-pyridylethylene) moiety due to its larger cavity
than that of HemiMeQ[6].
Furthermore, CX[4] exhibited fluorescence at 513 nm,
whereas its interaction with HemiMeQ[6] and HemiMeQ[7]
yielded almost the same fluorescence spectra, with only a slight
decrease in emission intensity (Supplementary Fig. S7). From
the change in fluorescence intensity, we inferred that the
inclusion complex was mainly formed with 1:1 stoichiometry.
The binding constants (K) of CX[4] with HemiMeQ[6] and
HemiMeQ[7] were estimated as to be 2.85×106 and 7.60×106
L·mol−1, respectively.41
A similar situation was observed in the interaction of
HemiMeQ[7] and CX[4] (Fig. 3), again indicating a rapid
exchange rate between binding and release of CX[4] on the
NMR timescale. The entire N-methyl-(4-pyridylethylene)
2.2.2. Interaction of CX[4] with HemiMeQ[6], HemiMeQ[7]
and Q[8] in water
Although interaction of CX[4] with the three selected Q[n]s,
namely HemiMeQ[6], HemiMeQ[7], and Q[8], were not
2

However, interaction of CX[4] with HemiMeQ[6] and
ACCEPTED MANUSCRIPT
HemiMeQ[7] yielded a slight decrease in fluorescence intensity,
with a small blue shift for both systems (Supplementary Fig.
S9). From the change in fluorescence intensity, we also inferred
that the inclusion complex was mainly formed with 1:1
stoichiometry. The binding constants (K) of CX[4] with
HemiMeQ[6] and HemiMeQ[7] were estimated to be 4.81×107
and 7.60×106 L·mol−1, respectively.41
2.3. Responses of the CX[4]-Q[8] system to certain organic
compounds
Kim and co-workers first confirmed that the cavity of Q[8] is
large enough to include two guest molecules simultaneously.42,43
Based on the interaction of CX[4] with HemiMeQ[6] and
HemiMeQ[7], the 4-pyridylethylene moiety on the CX[4]
molecule is likely included in the cavity of the selected Q[n]s.
Moreover, CX[4] forms
a 1:1 stoichiometry host-guest
interaction system with Q[8], and the fluorescence intensity of
CX[4] was dramatically enhanced upon complex formation,
suggesting that the two 4-pyridylethylene moieties of CX[4]
could be simultaneously included in the Q[8] cavity. This
inspired us to investigate the response of the CX[4]-Q[8]
interaction system to certain molecules by observing a change
in fluorescence intensity. Phenanthrene (G1) and molecules
with a similar structure such as 1,10-phenanthroline (G2)
enhanced fluorescence emission upon interaction with the
CX[4]-Q[8] system. In contrast, amantadine (G3) and its
derivatives (G4), and 4,7-dimethyl-1,10-phenanthroline (G5)
quenched fluorescence emission upon interaction with the
CX[4]-Q[8] system. For example, upon the addition of G1 to
the CX[4]-Q[8] system, a further dramatic enhancement in
fluorescence emission occurred, accompanied by a blue shift
from 530 nm to 514 nm (Fig. 5), and similar results were
obtained with G2 (Supplementary Fig. S10). Thus, fluorescence
of the CX[4]-Q[8] (1:1) solution was stimulated by G1, and
strong green fluorescence was observed by the naked eye under
365 nm UV irradiation (Fig. 5 inset). Further experiments
revealed that G1 exhibited fluorescence quenching when it
interacted with Q[8], indicating the formation of a novel π-π
stacking of the 4-pyridylethylene moiety and G1 in the Q[8]
cavity with 1:1:1 (Q[8]-CX[4]-G1) stoichiometry. Thus, the
CX[4]-Q[8] interaction system could be used as a fluorescence
probe to detect phenanthrene or compounds with similar
structures.
Fig. 3. Titration 1H NMR spectra (500 MHz, DMSOd6) of HemiMeQ[7] in
the presence of 0 (a), 0.30 (b), 0.70 (c), and 1.00 (d) equivalents of CX[4],
and (e) 1H NMR spectrum of neat CX[4] at 25°C.
1
directly observed by H NMR spectra due to poor solubility of
related species in neutral water, their fluorescence spectra
provide useful interaction information. In particular, interaction
between CX[4] with Q[8] was apparent (Fig. 4) because the
fluorescence intensity increased upon the addition of Q[8], and
the emission wavelength hypsochromically shifted from 503 to
530 nm. An approximately 3-fold enhancement in fluorescence
was observed upon the addition of 1 equivalent of Q[8],
accompanied by a colour change from cyan to yellow
(Supplementary Fig. S8). From the change in fluorescence
intensity, we inferred that the interaction product was mainly
formed with 1:1 stoichiometry (inset in Fig. 4). The interaction
constant (K) for the CX[4]-Q[8] complex was estimated to be
1.22×107 mol/L according to the literature.41
Fig. 5. Fluorescence spectra of the CX[4]-Q[8] complex upon the addition
of different equivalents of phenanthrene, accompanied by a colour change
from yellow to green (from 530 nm to 514 nm) in water.
Fig. 4. Fluorescence spectra (λex = 503 nm) of CX[4] (1×10-5M) in the
presence of 0 (a), 0.10 (b), 0.20 (c), 0.30 (d), 0.40 (e), 0.50 (f), 0.60 (g),
0.70 (h), 0.80 (i), 0.90 (j), 1.00 (k), 1.50 (l), 2.00 (m), 3.00 (n) and 4.00 (0)
equivalents of Q[8].
In contrast, addition of G3 to the CX[4]-Q[8] system
quenched the fluorescence emission and resulted in a blue shift
3

from 530 nm to 515 nm (Fig. 6). Thus, the fluorescence of the
A suspension of p-tert-butyl C[4]A (6.48 g, 10 mmol),
phenol (4.32 g, 46 mmol), and AlCl3 (8.0 g, 66 mmol) in
anhydrous toluene (60 mL) was stirred at room temperature for
2 h. After cooling, the reaction mixture was added to 100 mL of
hydrochloric acid solution (0.2 mol/L), the toluene layer was
separated, and solvent was evaporated in vacuo. The yellowish
product was suspended in MeOH (100 mL) and refluxed for 30
min. After cooling, the resulting precipitates were filtered to
ACCEPTED MANUSCRIPT
CX[4]-Q[8] (1:1) solution was diminished by G3, and weak
fluorescence could be observed by the naked eye under 365 nm
UV irradiation (Fig. 6 inset). Further experiments revealed that
derivatives of G4 and G5 exhibited similar quenching behaviour
(Supplementary Fig. S11 -12). We attribute the red shift in the
emission spectra to the formation of a new G3-Q[8] host-guest
inclusion complex that results in fluorescence quenching, and
CX[4]-Q[8] interaction systems could serve as useful
fluorescence probes for detecting related compounds.
1
afford product as a white powder: yield 2.64 g (76.6%). H
NMR (CDCl3) δ 9.45 (4H, s, ± OH), 7.61 (8H, d, J = 7.8,
aromatic-H), 6.75 (4H, t, aromatic-H), 4.27(s, 4H, Ar-CH2-Ar),
3.56(s, 4H, Ar-CH2-Ar), m/z 425.2 (M + H +).
4.2.2. 25,27-Bis(3-bromopropoxy)-26,28-dihydroxy
calix[4]arene
To a suspension of 25,26,27,28-tetrahydroxycalix[4]arene
(2.12 g, 5.00 mmol) in MeCN (250 mL) were added
1,3-dibromopropane (20.2 g, 100 mmol) and K2CO3 (3.45 g,
25.0 mmol). The reaction mixture was refluxed for 48 h. The
solvent and unreacted dibromopropane were then removed in
vacuo, and the residue was quenched with 5% HCl (100 mL)
and CHCl3 (200 mL). The organic phase was separated, washed
with water, and dried. The solvent was then distilled off, and the
oily residue was subjected to column chromatography
(CH2Cl2-petroleum ether (60-90 °C) 2:3) to give a white, pure
aim compound (2.30 g, 69%): mp 288−290 °C; 1H NMR
(CDCl3) δ 7.70 (s, 2H, OH), 7.15, 6.88 (s, 4H each, ArH), 4.27
(d, J = 13.0 Hz, 4H, ArCH2Ar), 4.12 (t, J = 7.8 Hz, 4H,
OCH2CH2CH2), 4.01 (t, J = 8.0 Hz, 4H, BrCH2CH2CH2), 3.35
(d, J = 13.0 Hz, 4H, ArCH2Ar), 2.53 (m, 4H, BrCH2CH2-CH2),
1.27 (s, 18H, CH3), 1.02 (s, 18H, CH3); 13C NMR (CDCl3) δ
150.7, 149.3, 147.4, 141.8, 132.8, 127.7, 125.5 (d), 77.1
(t),73.5, 34.0 (d), 33.6, 31.0, 31.8, 31.1, 30.3; MS, m/z 667.2 (M
+ H+).
Fig. 6. Fluorescence spectra of the CX[4]-Q[8] system upon addition of
different equivalents of amantadine, accompanied by a colour change from
yellow to green (from 530 nm to 515 nm) in water.
3. Conclusions
In summary, we have designed and synthesized a functionalised
calix[4]arene, namely 5,11-Di(N-methyl-(4-pyridylethylene))-
4.2.3. 5,11-Diformyl-25,27-Bis(3-bromopropoxy)-26,28-dihydr
oxycalix[4]arene
25,27-Bis(3-bromopropoxy)-26,28-dihydroxy
calix[4]arene
(CX[4]), in which the N-methyl-(4-pyridylethylene) moieties
can serve as a guest and interact with cucurbit[n]urils. Given the
solubility of CX[4], two DMSO-soluble guests, HemiMeQ[6]
and HemiMeQ[7], and unsubstituted Q[8] were selected to
investigate the interactions of these two types of macrocyclic
compounds. The results showed that the N-methyl-
(4-pyridylethylene) moieties on CX[4] can be included in the
cavity of the selected cucurbit[n]urils. In particular, the
interaction of CX[4] and Q[8] with 1:1 stoichiometry induced
an enhancement in fluorescence emission from cyan to light
yellow. Moreover, the CX[4]-Q[8] interaction system could
respond to certain compounds by fluorescence enhancement for
phenanthrene (G1) and molecules with similar structures such
as 1,10-phenanthroline (G2), or fluorescence quenching for
amantadine (G3), its derivatives (G4), and 4,7-dimethyl-
1,10-phenanthroline (G5), thereby serving as probes for
detecting these compounds.
25,27-Bis(3-bromopropoxy)-26,28-dihydroxycalix[4]arene
(3.33 g, 5.0 mmol)) was dissolved in 100 mL of dry chloroform
and the solution was kept under N2 and cooled to 0°C in an ice
bath. After 15 min, Cl2CHOCH3 (11.38 g, 0.1 mol) and TiCl4
(18.68 g, 0.1 mol) were added to the vigorously stirred solution.
After 1.5h, the reaction mixture was poured into 300 mL of 1 M
HCl and the solution was stirred for 2h. After the addition of 150
mL of CH2Cl2 to the solution, the organic phase was separated
and washed twice with water, dried over Na2SO4, and filtered.
The solvent was evaporated under reduced pressure and the
mixture three compounds was obtained after purification by
column chromatography (eluent: hex/EtOAc= 7:3) to give a pale
1
yellow solid, 2.07 g, yield 57 %: δ: mp 306−309°C; H NMR
(CDCl3) δ 9.789 (s, 2HꢀCHO), 8.892 (s, 2H, OH), 7.637(s, 4H,
ArH), 6.98 (d, J = 7.6 Hz, 4HꢀArH), 6.82 (t, 2H, ArH), 4.28 (d,
J = 13.2 Hz, 4H,ArCH2Ar), 4.18 (t, 4H, OCH2CH2CH2Br),
3.978 (t, 4H, OCH2CH2CH2Br), 3.543 (d, J = 13.2 Hz, 4H,
ArCH2Ar), 2.56 (m, 4H, OCH2CH2CH2Br); 13CNMR (CDCl3) δ
190.9, 159.2, 151.1, 132.3, 131.1, 129.7, 128.9, 128.5, 126.2,
74.0, 33.3, 31.3, 29.8; MS (FAB), m/z 745.2 (M + Na+).
4. Experimental Section
4.1. Materials and methods
All chemicals and solvents were used as supplied without
further purification. HemiMeQ[6] and HemiMeQ[7] were
synthesised according to our previous work,39 and Q[8] was
prepared according to the literature.6,7 1H NMR spectra were
recorded at 20°C on a Varian INOVA-400 spectrometer.
4.2.4. 5,11-Di(N-methyl-(4-pyridylethylene))-25,27-Bis(3-brom
opropoxy)-26,28-dihydroxycalix[4]arene
5,11-Diformyl-25,27-Bis(3-bromopropoxy)-26,28-dihydroxy
calix[4]arene (0.89 g, 6 mmol), N-methyl-4-methylpyridine
(500 mg, 2.12 mmol), and piperidine (0.6 mL) were mixed and
stirred in ethanol (20 mL) at 80°C for 8h. During the heating
process, the solution changed from pale yellow to dark purple.
After completion of the reaction, the mixtures were cooled to
0°C. The formed precipitate was filtered and washed with
4.2. Synthesis and characteristics
4.2.1. 25,26,27,28-tetrahydroxycalix[4]arene
4

28. Gutsche CD, Acc Chem Res. 1983; 16: 161.
29.
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5,11-Di(N-methyl-(4-pyridylethylene))-25,27-Bis(3-bromoprop
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oxy)-26,28 -dihydroxy calix[4]arene (0.368 g, 51.6 % yield). δ:
mp 239−242 °C; 1H NMR (CDCl3) δ 9.713 (s, 2H, OH), 8.74 (d,
J=10.8 Hz, 4H, C5H4N), 8.06 (d, J = 10.8 Hz, 4H, C5H4N), 7.80
(d, J = 16 Hz, 2H, CH=CH), 7.63 (s, 4H, ArH), 7.29 (d, J = 16
Hz, 2H, CH=CH), 7.11 (d, J = 8 Hz, 4H, ArH), 6.84 (t, 2H,
ArH), 4.175 (s, 3H, N-CH3), 4.270−4.028 (m, 19H, ArCH2Ar,
OCH2CH2CH2Br, N-CH3), 3.547 (d, J = 13.2 Hz, 4H,
ArCH2Ar); 13C NMR (CDCl3) δ 150.7, 149.3, 147.4, 141.8,
132.8, 127.7, 125.5 (d), 77.1 (t),73.5, 34.0 (d), 33.6, 31.0, 31.8,
31.1, 30.3; MS (FAB), m/z 1157.57 (M + H +).
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (Nos. 21601090, 51663005, 21761007).
and the Natural Science Foundation of Jiangsu Province (Grant
No.BK20160943). The study was also supported by the Startup
Foundation of Nanjing University of Information Science &
Technology (2015r047).
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