Synthesis of copillar[5]arenes and their host-guest complexation with two types of guests

Article abstract of DOI:10.1002/cjoc.201400893

A series of novel copillar[5]arenes 1a-1f containing different substituents were synthesized. And their complexation with two types of guests was investigated. For symmetrical guests, 1,4-dibromobutane (DBB) could thread in the cavity of copillar[5]arenes to form inclusion complexes. But for the unsymmetrical guests, copillar[5]arene 1f bearing 4-(naphthalen-1-yloxy)butoxy could not complex with sec-butyl iodide (SBI) and sec-butyl bromide (SBB) at all, while 1f showed weak interaction with sec-butylamine·HCl (SBA) outside the cavity. These results indicated that the modified group of copillar[5]arene and the symmetry of guest played an important role in the complexation model and selectivity.

Full text of DOI:10.1002/cjoc.201400893

FULL PAPER
DOI: 10.1002/cjoc.201400893
Synthesis of Copillar[5]arenes and Their Host-Guest
Complexation with Two Types of Guests
a
,a
,a
b
a
Hongfei Huang, Luzhi Liu,* Wengui Duan,* Yan Huang, and Guishan Lin
a
School of Chemistry and Chemical Engineering, Guangxi University & Guangxi Experiment Centre of Science
and Technology, Nanning, Guangxi 530004, China
b
Guangxi Institute of Traditional Medical and Pharmaceutical Science, Nanning, Guangxi 530022, China
A series of novel copillar[5]arenes 1a－1f containing different substituents were synthesized. And their com-
plexation with two types of guests was investigated. For symmetrical guests, 1,4-dibromobutane (DBB) could
thread in the cavity of copillar[5]arenes to form inclusion complexes. But for the unsymmetrical guests, copillar-
[
5]arene 1f bearing 4-(naphthalen-1-yloxy)butoxy could not complex with sec-butyl iodide (SBI) and sec-butyl
bromide (SBB) at all, while 1f showed weak interaction with sec-butylamine•HCl (SBA) outside the cavity. These
results indicated that the modified group of copillar[5]arene and the symmetry of guest played an important role in
the complexation model and selectivity.
Keywords copillar[5]arenes, synthesis, complexation selectivity, host-guest chemistry
Introduction
amine•HCl and octadecylamine•HCl, but 1,4-bis-
butoxy)pillar[5]arene did not form such complex at all.
(
Pillar[n]arenes, a new type of macrocyclic hosts,
para-bridged analogues of calixarenes, have attracted
considerable attention owing to their applications in
host-guest chemistry,
material chemistry,
However, very little is known about the complexation
selectivity for non-symmetrical pillar[5]arenes, es-
[30]
pecially the monofunctionalized copillar[5]arene,
[
1-4]
[5-7]
self-assembly chemistry,
although this type of structure has become the central
topic of many studies because of their easy functionali-
[
8-11]
[12-14]
photochemistry,
fluores-
As pil-
[
15-21]
[22,23]
cence chemistry,
and biochemistry.
[31,32]
zation and different self-assembly behavior.
lararenes show high symmetrical and rigid pillar-like
structure and have rich electron density, they exhibit
excellent host-guest binding properties for a variety of
neutral and electron accepting molecules by weak non-
covalent interactions (van der Waals, CH-π, cation-π,
OMe
OR
H
H
[
24-26]
4
H-bonding, etc.).
Importantly, the complexation
H
H
MeO
MeO
selectivity of pillararenes towards guest molecules can
be tuned by varying the shape and size of the cavity or
modifying the substituents on the upper and lower rims.
A complete complexation selectivity was found between
pillar[5]- and pillar[6]arenes with alkyl bromides due to
1
1h
a
－
:
1f
R = C H10Br
6
MeP5: R = Me
e
b
a
d
b
Br
R
[
27]
Br
c
a
their different size of cavity.
Considering the small
size cavity of pillar[5]arene among other analogues,
guest molecules have to be carefully selected for host-
[28]
guest complexation study. Hou et al.
developed a
class of artificial transmembrane channels from peptide-
appended pillar[n]arenes (n＝5, 6), and some of them
had chiral selectivity for amino acid enantiomers. Re-
R = I,
R = Br,
R = NH +Cl , SBA
SBI
DBB
SBB
-
3
[29]
cently, we reported
arenes with different alkyl chains, in which 1,4-bis-
methoxy)pillar[5]arene (MeP5, Figure 1) displayed
strong complex with sec-butylamine•HCl, dodecyl-
the fully symmetrical pillar[5]-
Figure 1 Structures of (co)pillar[5]arene hosts and two types of
guests.
(
[
30,33-40]
In previous work,
we have known that pil-
*
E-mail: llzh068@163.com; wgduan@gxu.edu.cn
Received December 30, 2014; accepted January 28, 2015; published online XXXX, 2015.
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/cjoc.201400893 or from the author.
Chin. J. Chem. 2015, XX, 1—5
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1

Huang et al.
FULL PAPER
lar[5]arenes or biphen[n]arenes, which were first re-
were performed on a TSQ Quantum Access MAX
HPLC-MS instrument (Thermo Scientific Co., Ltd.,
USA).
[41]
ported by Li et al.
in 2015, showed good binding
properties to the symmetrical guests such as the linear
α,ω-dihaloalkane, α,ω-dihydroxyalkane and α,ω-di-
aminoalkane by the two interactions of the cavity. In
contrast, the unsymmetrical guests possessing one
binding site always showed weak or no interaction. The
different binding ability between these two types of
guests would lead to their complexation selectivity or
different complexation model. However, until now, this
type of guests may not be feasible and have received
less attention. Herein, we synthesized a series of novel
copillar[5]arenes bearing different groups (Scheme 1) as
model hosts and selected dibromoalkane (DBB),
sec-butyl iodide (SBI), sec-butyl bromide (SBB) and
sec-butylamine•HCl (SBA) (Scheme 1) as model guests
to investigate their complex properties.
General procedure for the preparation of copillar-
[
5]arenes
To a solution of 2 (200 mg, 0.27 mmol) and K
55 mg, 0.40 mmol) in DMF (5 mL), the corresponding
2
CO
3
(
bromoalkane derivative 3 or 4 (0.33 mmol) was added
under a nitrogen atmosphere and the mixture was stirred
at 90 ℃. After the completion of the reaction, water (50
mL) was added and the product was extracted with ethyl
acetate (20 mL×3). The combined organic phase was
dried over anhydrous Na SO . The crude mixture was
2 4
chromatographed over silica gel column using a mixture
of ethyl acetate and petroleum ether.
1a: white solid, in 81.1% yield (240 mg), m.p. 93－
1
9
4 ℃; H NMR (600 MHz, CDCl
3
, 298 K) δ: 7.19 (d,
Scheme 1 Synthesis of novel copillar[5]arenes 1a－1f
J＝8.4 Hz, 1H), 7.03 (d, J＝7.8 Hz, 1H), 6.89 (s, 1H),
6
6
2
1
1
1
3
.81－6.73 (m, 10H), 4.19－4.13 (m, 2H), 3.88 (t, J＝
.0 Hz, 2H), 3.80－3.76 (m, 10H), 3.67－3.63 (m, 27H),
.91－2.87 (m, 2H), 2.86－2.81 (m, 1H), 2.32 (d, J＝
2.0 Hz, 1H), 2.28 (dd, J＝12.6, 1.8 Hz, 1H), 1.87－
.86 (m, 5H), 1.80－1.76 (m, 2H), 1.74－1.71 (m, 1H),
.66 (d, J＝9.6 Hz, 1H), 1.51－1.42 (m, 2H), 1.30 (s,
Br
R
n
OMe
OMe
H
3, 4
H
H
4
H
1
3
MeO
HO
H), 1.24 (s, 3H), 1.23 (d, J＝3.0 Hz, 6H); C NMR
150 MHz, CDCl , 298 K) δ: 178.74, 150.97, 150.92,
2
(
3
1
1
1
6
4
50.86, 149.97, 147.02, 145.90, 134.78, 128.59, 128.43,
28.42, 128.41, 128.37, 128.27, 127.09, 124.36, 124.13,
15.16, 114.30, 114.25, 114.22, 114.12, 114.03, 68.03,
4.47, 55.99, 55.93, 55.90, 55.88, 55.81, 53.12, 47.83,
5.00, 38.10, 37.13, 36.84, 33.61, 29.96, 29.75, 29.47,
OMe
OMe
H
H
H
4
H
MeO
O
26.64, 25.89, 25.40, 24.12, 21.94, 18.77, 16.69; ESI-MS
＋
＋
n
R
m/z: 1091.88 ([M ＋H] ), 1108.11 ([M ＋NH
4
] ),
＋
1
129.03 ([M＋K] ).
1
b: white solid, in 84.3% yield (245 mg), m.p. 90－
1
a: n = 4
b: n = 5
c: n = 6
d: n = 8
1
1
1
1
3
92 ℃; H NMR (600 MHz, CDCl , 298 K) δ: 7.17 (d,
J＝8.4 Hz, 1H), 7.01 (dd, J＝8.4, 1.2 Hz, 1H), 6.87 (d,
J＝1.2 Hz, 1H), 6.79－6.74 (m, 10H), 4.15－4.04 (m,
R =
O
∗
2
3
H), 3.84 (t, J＝6.0 Hz, 2H), 3.78－3.76 (m, 10H),
.66－3.63 (m, 27H), 2.89－2.86 (m, 2H), 2.84－2.80
O
∗
1e: n = 4, R =
(m, 1H), 2.30 (d, J＝12.0 Hz, 1H), 2.26 (dd, J＝12.6, 2.4
Hz, 1H), 1.83－1.79 (m, 2H), 1.79－1.70 (m, 5H),
1
1
.65－1.57 (m, 3H), 1.51－1.42 (m, 3H), 1.27 (s, 3H),
.23 (s, 3H), 1.22 (s, 3H), 1.21 (s, 6H); C NMR (150
∗
1
3
1f: n = 4, R =
MHz, CDCl , 298 K) δ: 178.76, 151.97, 150.95, 150.94,
3
1
1
1
50.92, 150.90, 150.12, 147.05, 145.88, 134.81, 128.52,
28.42, 128.40, 128.36, 128.34, 128.28, 127.08, 124.35,
24.09, 115.08, 114.28, 114.24, 114.14, 114.10, 68.32,
Experimental
Pillar[5]arene 2 and bromoalkane derivatives 3, 4
64.58, 55.97, 55.89, 55.86, 55.81, 53.33, 47.79, 44.95,
38.09, 37.11, 36.81, 33.60, 30.29, 29.95, 29.87, 29.77,
were synthesized according to the literature proce-
[42,43]
dure
and copillar[5]arene 1h was previously syn-
29.60, 29.52, 28.73, 25.38, 24.14, 24.11, 23.01, 21.91,
＋
thesized. Solvents were either employed as purchased or
dried according to the procedures described in the lit-
erature. H NMR (600 MHz) and C NMR (150 MHz)
spectra were recorded on an Av-600 spectrometer
18.75, 16.66; ESI-MS m/z: 1104.95 ([M] ), 1122.12
([M＋NH ] ), 1142.90 ([M＋K] ).
4
＋
＋
1
13
1c: white solid, in 85.1% yield (250 mg), m.p. 88－
1
89 ℃; H NMR (600 MHz, CDCl , 298 K) δ: 7.19 (d,
3
(
Brucker Co., Ltd., Switzerland) by using CDCl
3
as
J＝8.4 Hz, 1H), 7.02 (d, J＝8.4 Hz, 1H), 6.89 (s, 1H),
6.81－6.77 (m, 10H), 4.10－4.05 (m, 2H), 3.84 (t, J＝
solvent and TMS as an internal standard. Mass spectra
2
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Chin. J. Chem. 2015, XX, 1—5

Synthesis of Copillar[5]arens and Their Host-Guest Complexation with Two Types of Guests
6.0 Hz, 2H), 3.80－3.78 (m, 10H), 3.67－3.65 (m, 27H),
2.89－2.88 (m, 2H), 2.85－2.81 (m, 1H), 2.32 (d, J＝
12.0 Hz, 1H), 2.27 (dd, J＝12.6, 1.2 Hz, 1H), 1.88－1.77
135.93, 129.76, 129.70, 129.65, 129.62, 129.57, 128.90,
127.82, 127.31, 127.08, 126.56, 123.38, 121.58, 116.37,
115.60, 115.53, 115.46, 115.45, 115.41, 105.92, 33.31,
(
m, 5H), 1.75－1.70 (m, 1H), 1.68－1.65 (m, 3H),
31.19, 31.15, 31.10, 31.04, 30.97, 30.82, 28.15, 27.74,
＋
1
1
.56－1.51 (m, 2H), 1.46－1.39 (m, 4H), 1.29 (s, 3H),
24.09, 15.55; ESI-MS m/z: 934.57 ([M] ), 951.64
([M＋NH ] ), 956.62 ([M＋Na] ).
4
13
＋
＋
.24 (s, 3H), 1.23 (d, J＝3.6 Hz, 6H); C NMR (150
, 298 K) δ: 178.78, 150.96, 150.92, 150.91,
50.88, 150.87, 150.17, 147.08, 145.88, 134.83, 128.54,
MHz, CDCl
3
1
1
1
1
5
2
2
Results and Discussion
28.50, 128.40, 128.38, 128.35, 128.33, 128.28, 127.09,
24.37, 124.10, 115.09, 114.27, 114.224, 114.21,
14.13, 114.09, 68.54, 64.69, 55.98, 55.92, 55.85, 55.82,
3.11, 47.80, 44.95, 38.12, 37.12, 36.81, 33.60, 30.30,
9.93, 29.86, 29.74, 29.50, 28.85, 26.20, 26.08, 25.39,
4.15, 24.13, 21.91, 18.77, 16.68; ESI-MS m/z: 1135.90
1
Figure 2 showed the H NMR spectra of DBB in
CDCl in the absence and in the presence of approxi-
3
−1
mately 1 equiv. of host 1a (18.8 mmol•L ). The protons
of DBB showed very substantial upfield shift (Δδ＝3.18
b
for H ) as well as broadening effects in the presence of
＋
＋
(
[M＋NH
4
] ), 1157.98 ([M＋K] ).
1a compared to that of free DBB. Meanwhile, the pro-
ton signals of aromatic region and methoxy of 1a dis-
played downfield displacement. This result indicated
that DBB was locked in the cavity. In contrast to 1a,
copillar[5]arene 1h could form intramolecular or inter-
molecular self-assembled structures. On the basis of the
understanding of the binding ability between α,ω-di-
haloalkane and one haloalkane, our particular interest is
to know whether 1h could further complex with DBB.
After complexing, the protons of DBB exhibited a larger
upfield shift, while the alkyl bromide protons of 1h
shifted downfield (see Supporting Information Figure
S31), which indicated that the protons of DBB were
located in the deshielding region of the cyclic pillar
structure, and the alkyl bromide protons of 1h were
squeezed outside the cavity.
1
d: white solid, in 83.4% yield (252 mg), m.p. 70－
1
7
3
1 ℃; H NMR (600 MHz, CDCl , 298 K) δ: 7.20 (d,
J＝8.4 Hz, 1H), 7.03 (d, J＝8.4 Hz, 1H), 6.91 (s, 1H),
6
6
2
1
1
2
1
.80－6.77 (m, 10H), 4.11－4.02 (m, 2H), 3.85 (t, J＝
.0 Hz, 2H), 3.81－3.78 (m, 10H), 3.67－3.65 (m, 27H),
.90－2.89 (m, 2H), 2.87－2.84 (m, 1H), 2.33 (d, J＝
2.0 Hz, 1 H), 2.32 (d, J＝12.0 Hz, 1 H), 1.89－1.84 (m,
H), 1.80－1.77 (m, 4H), 1.73 (brs, 1H), 1.69－1.65 (m,
H), 1.62－1.60 (m, 1H), 1.52－1.50 (m, 3H), 1.45－
.43 (m, 1H), 1.36－1.34 (m, 3H), 1.30 (brs, 8H), 1.25
13
(
s, 3H), 1.24 (d, J＝3.3 Hz, 6H); C NMR (150 MHz,
CDCl , 298 K) δ: 178.44, 151.62, 150.57, 150.49,
49.89, 146.74, 145.52, 134.50, 128.15, 128.12, 128.07,
3
1
1
1
5
3
2
2
1
28.05, 128.01, 127.97, 127.92, 126.73, 124.02, 123.74,
14.80, 113.94, 113.90, 113.83, 68.28, 64.48, 55.61,
5.57, 55.55, 55.49, 47.44, 44.60, 37.78, 36.77, 36.45,
3.25, 31.70, 29.95, 29.57, 29.50, 29.48, 29.45, 29.42,
9.24, 29.22, 29.18, 28.96, 28.46, 26.04, 25.69, 25.03,
3.78, 22.47, 21.55, 18.43, 16.32, 13.92; ESI-MS m/z:
＋
＋
147.40 ([M＋H] ), 1164.10 ([M＋NH
4
] ), 1168.98
＋
([M＋Na] ).
1
e: white solid, in 89.4% yield (214 mg), m.p. 124－
1
1
3
25 ℃; H NMR (600 MHz, CDCl , room temperature)
δ: 7.31－7.27 (m, 2H), 6.95 (t, J＝7.2 Hz, 1H), 6.91 (d,
J＝7.8 Hz, 2H), 6.80－6.76 (m, 10H), 4.03 (t, J＝6.0
Hz, 2H), 3.91 (t, J＝6.0 Hz, 2H), 3.81－3.77 (m, 10H),
1
3
3
.67－3.64 (m, 27H), 2.90－2.89 (m, 4H); C NMR
(
150 MHz, CDCl , 298 K) δ: 160.40, 152.26, 152.23,
3
1
1
1
5
3
52.21, 151.42, 130.88, 129.72, 129.67, 129.64, 129.61,
29.59, 129.56, 122.05, 116.33, 115.84, 115.59, 115.56,
15.53, 115.49, 115.45, 115.43, 69.41, 68.78, 57.25,
7.19, 57.16, 57.15, 33.32, 32.86, 31.61, 31.15, 31.10,
1.05, 30.97, 30.80, 27.89, 27.71, 24.09, 15.54; ESI-MS
＋
＋
1
m/z: 884.59 ([M] ), 901.78 ([M＋NH
4
] ), 906.72
Figure 2 H NMR spectra (600 MHz, CDCl , 298 K) of (a)
3
＋
＋
(
[M＋Na] ), 922.66 ([M＋K] ).
DBB, (b) 1a, and (c) an equimolar mixture of 1a and DBB (18.8
mmol•L ).
−
1
1
f: white solid, in 95.8% yield (242 mg), m.p. 129－
1
1
3
30 ℃; H NMR (600 MHz, CDCl , 298 K) δ: 8.29 (d,
J＝8.4 Hz, 1H), 7.81 (d, J＝7.8 Hz, 1H), 7.50－7.43 (m,
H), 7.38 (t, J＝8.4 Hz, 1H), 6.83－6.75 (m, 11H), 4.23
The host-guest complexation of DBB with 1b－1f
3
containing different substituents, was also investigated.
1
(
(
t, J＝6.0 Hz, 2H), 3.98 (t, J＝6.0 Hz, 2H), 3.83－3.77
m, 10H), 3.66－3.61 (m, 27H), 2.20－2.14 (m, 2H),
Table 1 showed the observed H NMR up-field shifts Δδ
of the guests in host-guest system. The large chemical
13
b
2
.11－2.06 (m, 2H); C NMR (150 MHz, CDCl
3
, 298
shift Δδ of H indicated that all the designed copil-
K) δ: 156.13, 152.25, 152.21, 152.19, 152.17, 151.42,
lar[5]arenes displayed excellent complex properties with
Chin. J. Chem. 2015, XX, 1—5
© 2015 SIOC, CAS, Shanghai, & WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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3

Huang et al.
FULL PAPER
the symmetrical guest DBB. Compared with the other
copillar[5]arenes, binding properties varied significantly
by the type and side chain length of the substituent
groups. Copillar[5]arenes possessing dehydroabietic acid
group showed a better binding properties than those hav-
ing phenyl or naphthyl group, and the copillar[5]arene 1a
bearing the dehydroabietic acid group with an alkyl chain
having 4 carbon atoms showed the best binding property
with DBB. In addition, in contrast to the full symmetrical
pillar[5]arene MeP5 (its Δδ value was 2.5 in MeP5-DBB
complex), these hosts except 1f had stronger binding
abilities according to the Δδ values, which increased in
the order of 1f＜MeP5＜1d＜1e＝1b＜1c＜1a. This
result suggested that the suitable substituent on the ring of
pillar[5]arene could improve their binding properties in
host-guest system, although the substituents were larger
and longer.
guests were deduced as shown in Figure 4. It should be
emphasized that pillar[5]arene could complex with ter-
minal one haloalkane such as 1h, which could form
self-complex by its side chain and cavity. But for the
nonterminal one haloalkane, copillar[5]arene did not
form such complex, leading to the complexation selec-
tivity between these two types of guests. On the other
hand, the full symmetrical pillar[5]arene MeP5 could
bind the guest SBA. However, when the alkyl substitu-
ent was bulkier than methyl group, such complex was
not formed, even though the group was replaced by
ethyl substituent. But for copillar[5]arene, the intro-
duced larger and longer substituent such as 4-(naph-
thalen-1-yloxy)butyl group as side chain, could complex
with SBA, indicating the good advantage of copil-
lar[5]arene for their host-guest properties toward this
type of guest.
[33]
To examine the influence of the different symmetri-
cal guests on the binding interactions and avoid the in-
terruption by the alkyl chain proton of host, we studied
the complexation of 1f with other guests SBI, SBB and
SBA. Interestingly, their binding behaviors in host-guest
system were very different. 1f showed no complexation
Table 1 Upfield shifts of two types of guest molecules ([G]＝
−
1
1
tion
3
8.8 mmol•L , CDCl , 298 K) in different host-guest complexa-
a
Guest Proton Δδ(1a) Δδ(1b) Δδ(1c) Δδ(1d) Δδ(1e) Δδ(1f)
b
with SBI and SBB in CDCl
3
, and its interaction with
DBB
H
H
3.18
2.93
2.96
2.85
2.93
2.45
SBA was weaker than DBB in accordance to smaller
a
0.05
1
-4
upfield shifts (Table 1). The signals of the protons (H )
of 1f remained nearly unchanged (Figure 3), that is, 1f
did not form an inclusion complex with SBA. This re-
sult was further proved by the 2D NOESY analysis (see
Supporting Information Figure S35). NOE correlations
were not observed between the protons of 1f and the
alkyl protons of SBA, suggesting that the alkyl group
was outside rather than into the cavity of 1f.
b
H
0.06
c
SBA
H
－
－
－
－
－
0－0.17
d
H
H
0.05
e
0.02
0
b
H
c
SBI
H
－
－
－
－
－
－
－
－
－
－
0
d
H
H
0
b
c
0
SBB
H
0
d
H
0
a
－
: The binding property between the host and guest was not
tested.
DBB
SBA
SBI, SBB
1
Figure 3 H NMR spectra (600 MHz, CDCl
3
, 298 K) of (a)
SBA, (b) 1f, and (c) an equimolar mixture of 1f and SBA (18.8
−
1
mmol•L ).
Based on the information gained from the above re-
sults, the complexation models of copillar[5]arenes with
Figure 4 The complexation models of copillar[5]arenes with
guests.
4
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Synthesis of Copillar[5]arens and Their Host-Guest Complexation with Two Types of Guests
Conclusions
[14] Ogoshi, T.; Yamafuji, D.; Aoki, T.; Yamagishi, T. J. Org. Chem.
011, 76, 9497.
2
In summary, we synthesized a series of novel copil-
lar[5]arenes bearing different groups and studied their
complexation with two types of guests DBB, SBI, SBB
and SBA. For symmetrical guests, DBB can thread in
the cavity of copillar[5]arenes to form inclusion com-
plexes. The binding ability of copillar[5]arenes in-
creases in the order of 1f＜1d＜1e＝1b＜1c＜1a. But
for the unsymmetrical guests, 1f can not complex SBI,
SBB at all, and shows weak interaction with SBA. Fur-
thermore, the binding models of copillar[5]arene be-
tween DBB and SBA are very different. Such com-
plexation selectivity would lead to the application of
copillar[5]arene for recognition and extraction of the
symmetrical dibromoalkane in organic media.
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Acknowledgement
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We are grateful to the National Natural Science
Foundation of China (No. 21402033), the Guangxi
Natural Science Foundation of China (No.
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013GXNSFBA019033), the Guangxi Experiment Cen-
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and the Scientific Research Foundation of Guangxi
University (No. XBZ130017).
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Chin. J. Chem. 2015, XX, 1—5
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