Mild Synthesis of Pillar[4]arene[1]cis-diepoxy-p-dione and Guest-Assisted Formation of a 2D Network in the Solid State

Article abstract of DOI:10.1002/ejoc.201701374

Herein, we developed an environmentally friendly, feasible method to synthesize pillar[4]arene[1]cis-diepoxy-p-dione. Strikingly, single-crystal X-ray analysis of pillar[4]arene[1]cis-diepoxy-p-dione and 5-chloropentanenitrile indicated a 1:2 stoichiometry to form a 2D network in the solid state.

Full text of DOI:10.1002/ejoc.201701374

A Journal of
Accepted Article
Title: Mild synthesis of pillar[4]arene[1]cis-diepoxy-p-dione and guest-
assisted formation of 2D network in solid state
Authors: Chengyou Han, Shengyi Dong, Dezhi Zhao, and Daofeng
Sun
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Eur. J. Org. Chem. 10.1002/ejoc.201701374
Link to VoR: http://dx.doi.org/10.1002/ejoc.201701374
Supported by

European Journal of Organic Chemistry
10.1002/ejoc.201701374
COMMUNICATION
Mild synthesis of pillar[4]arene[1]cis-diepoxy-p-dione and guest-
assisted formation of 2D network in solid state
[
a]
[b]
[a]
[a]
Chengyou Han,* Shengyi Dong, Dezhi Zhao, and Daofeng Sun*
Abstract: Herein we have developed an environmentally friendly
feasible method to synthesize pillar[4]arene[1]cis-diepoxy-p-dione.
Strikingly, X-ray single crystal analysis between pillar[4]arene[1]cis- Results and Discussion
diepoxy-p-dione and 5-chloropentanenitrile indicates an 1 : 2
stoichiometry to form 2D network in solid state.
Pillar[4]arene[1]quinone (H2) was synthesized according to the
4 2 3 6
reported literature by using Ce(NH ) (NO ) as the oxidizing
agent in THF/H O solution of DMpillar[5]arene (H1) at room
2
temperature (Scheme 1).9 As reported by us,8 the
pillar[4]arene[1]cis-diepoxy-p-dione (H3) was synthesized by
using tert-butyl hydroperoxide (t-BuOOH) as the oxygenation
agent and DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as base in
Introduction
More and more attention has been paid to design and synthesis
of new macrocyclic hosts since the four well-known classical
1
2
3
macrocycles, that are crown ethers, cyclodextrins, calixarenes
2 2
dry CH Cl solution in an ice bath. With the current emphasis on
and cucurbiturils,4 have played a major role in supramolecular
chemistry and are widely applied in different fields. Pillararenes,5
firstly reported in 2008, are one of leading candidates as a novel
kind of macrocyclic host, and they form versatile host‒guest
complexes with organic and inorganic cations, and with neutral
organic guests due to their highly symmetrical rigid
architectures.6 A series of functionalized pillararene derivatives
have been prepared to expand their applications in different
“green chemistry”, the search for novel oxidation agent and base
with environment-friendly affinities is remarkably important.
2 2 2
Luckily, we found that H O , which transforms into H O after
decomposition, can be used as oxidation agent while NaHCO
3
,
can be used as the inorganic base instead of the organic DBU
base in this reaction. Meanwhile, the reaction can be done in
ethanol/H
2
O at room temperature instead of CH
2
Cl
2
in an ice
the
bath. Generally,
we successfully synthesized
areas.7 Recently, we have synthesized
pillar[5]arene derivative, pillar[4]arene[1]cis-diepoxy-p-dione, by
base-promoted direct addition of molecular oxygen
oxygenation) to the pillararene benzoquinone rings. It showed
a new kind of
pillar[4]arene[1]cis-diepoxy-p-dione (H3) under milder and more
green conditions than before.
8
(
good complexations with dinitrile molecules in chloroform and in
the solid state. However, environmentally unfriendly reagents
including tert-butyl hydroperoxide as the oxygenation agent and
DBU (1,8-diazabicyclo[5.4.0]undec-7-ene) as the base are used
during the epoxidation. In order to improve the epoxidation in an
environmentally friendly way and to further investigate its
host‒guest property different from pillar[5]arene and
pillar[4]arene[1]quinone, it is necessary to develop a feasible
method with environmentally friendly reagents and explore its
host‒guest complexation with different molecules.
Hence, in this communication, we explore the improved
synthesis of pillar[4]arene[1]cis-diepoxy-p-dione by using H
2 2
O
as the oxygenation agent and NaHCO as the base. Meanwhile,
3
its host‒guest properties with the unsymmetrical guest 5-
chloropentanenitrile both in solution and in solid state were also
investigated.
Scheme 1. Synthetic route for pillar[4]arene[1]cis-diepoxy-p-dione (H3)
[
a]
Dr. C. Han, Dr. D. Zhao, Prof. Dr. D. Sun
Department of Chemistry, College of Science
China University of Petroleum (East China)
No. 66, Changjiang West Road, Huangdao District, Qingdao, China,
The host‒guest properties of pillar[4]arene[1]cis-diepoxy-
p-dione (H3) have been explored, and we found it can
effectively complex with dinitrile alkanes in our previous
work. After epoxidation, the symmetry of the host
molecules have changed from D5h for H1 into C for H3. In
2
266580
E-mail: hanchengyou@upc.edu.cn; dfsun@upc.edu.cn
Prof. Dr. S. Dong
[
b]
8
College of Chemistry and Chemical Engineering
Hunan University
order to expand the host‒guest properties of H3 with
different guest molecules, the unsymmetrical molecules 5-
Changsha, Hunan, 410082, P. R. China
Supporting information for this article is given via a link at the end of
the document.
chloropentanenitrile (G1) and 5-azidopentanenitrile (G2
were applied. Firstly, the host‒guest complexations were
)
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European Journal of Organic Chemistry
10.1002/ejoc.201701374
COMMUNICATION
investigated by 1H NMR spectra. The 1H NMR spectra
The association constants of these 1:1 complexes HnGn in
chloroform-d were also determined. We found that G1/G2 had
strong binding affinity with the host DMP5 (H1), which were
(
spectra b and d in Figure 1) of an equimolar solution of H3
and G1 G2 in chloroform-d show only one group of peaks
at NMR time scale, indicating fast-exchange complexation
between H3 and G1 G2 at 22 C. After complexation with
G1 and G2, phenyl protons H methylene protons H and
/
4
3
-1
(1.00 ± 0.40) × 10 for G1 and (3.70 ± 1.39) × 10 M for G2 in
/

3
,8
7
CDCl /CD COCD (9/1, v/v), indicating the effective
3
3
3
1
2
complexations of H1 with G1/G2. This is reasonable because
the host H1 has strong binding with dinitrile alkane guest
molecules which also have the electron-withdrawing cyano
methyl protons H on H3 shifted slightly downfield (spectra
c and d in Figure 1). Other protons on H3 also showed
minor downfield chemical shift changes after complexation.
a-d
The significant chemical shift upfield changes of H from
e-h
groups at the two ends of the alkyl chains as reported by Li et
al.10 Since the host molecule H2 has an electron-deficient
G1 and H from G2 were observed after complexation with
H3, which showed these methylene protons are located in
repeating unit benzoquinone, it has an electron-rich cavity with
negative electrostatic potential due to the four 1,4-
dimethoxybenzene units. Thus, it also can complex with G1/G2
just like pillar[5]arenes. But the association constants between
H2 and G1/G2 are smaller comparing with H1. The
complexations between H3 and G1/G2 are the weakest one
among these three host molecules, 11.4 ± 2.4 M-1 for G1 and
the shielding region of the cyclic pillar structure. This was
indicative of that the linear guest G1/G2 was threaded
through the cavity of cyclic host H3 to form
[
a
2]pseudorotaxane in solution with the methylene protons
a-d
e-h
H
and H in the cavity of H3. The above phenomena
suggested the effective bindings between H3 and guests
G1 G2
/
.
1
0.9 ± 4 M-1 for G2. This may because the host H3 become
flexible after the introduction of the cis-diepoxy-p-dione unit.
These three macrocyclic host molecules showed different
host‒guest properties although they had similar structures.
H12
H4
H9
H10
H
H2
H
H6
H7
H
H1
O
O
O
O
O
H
O
H
Table 1. K
a
values for complexations of G1 and G2 with H1‒H3 at room
H
H
H11
O H
H
H
temperature determined by an NMR titration method.
O
H8
O
O
O
H3
O
H5
-
1
Guests
G1
Hosts
a
K (M )
Hf
Hg
Hh He
N
Hb Hc
N
H1[a]
(1.00 ± 0.40) × 104
84.5 ± 6.3
Cl
N
3
Hd Ha
G1
G2
H2[b]
G1
G1
H3[b]
H1[a]
H2[b]
H3[b]
11.4 ± 2.4
G2
(3.70 ± 1.39) × 103
173.3 ± 10.3
10.9 ± 4
G2
G2
[
a] The
K
a
was determined in CDCl
3
/CD
3
COCD
3
(9/1, v/v) at room
temperature. [b] The K was determined in CDCl at room temperature.
a 3
Single crystal analyses are a very powerful tool to reveal the
molecular recognition and interactions between hosts and guest
molecules in the solid state. Single crystals of H3G1 were
grown by slow evaporation of their dichloromethane/methanol
(
v/v, 1/1) solution at room temperature (Figure 2 and Figure 3).
The formation of the included [2]pseudorotaxane structure
between H3 and G1 was verified by the crystal structure. Just
8
like the complexation between H3 and 1,4-dinitrile butane, G1
Figure 1. Partial 1H NMR spectra (400 MHz, CDCl
, 22 °C) of (a) 2 mmol of
3
locates in the cavity of H3. This is consistent with the proton
NMR discussion result that the protons Ha-d show conspicuous
upfield chemical shift changes after the occurrence of
complexation between H3 and G1. This [2]pseudorotaxane-like
structure is stabilized by multiple C-H•••π interactions (Figure 2,
a‒d, f‒h) between the methylene protons Hb,c on G1 and the π
systems of the benzene rings, and one C-H•••O hydrogen bond
interaction (Figure 2, e) between proton H3 on the G1 and
oxygen atom of the C=O double bonds of the cis-diepoxy-p-
dione rings. Because of the existences of the cyano groups in
the guest molecules G1/G2, dipole-dipole forces should also
G1; (b) 2 mmol of G1+H3; (c) 2 mmol of H3; (d) 2 mmol of G2+H3; (e) 2 mmol
of G2.
We then turn to study the affinities between different hosts
and guests molecules. By an NMR titration method, we
investigated the complexations between Hn (n = 1‒3) and Gn (n
=
1‒2) in detail (Figure S5‒S17). All the association constants
were calculated based on NMR data (Table 1) and all the molar
ratio plots indicated that the complexation stoichiometries
between Hn and Gn were 1 : 1 to form [2]pseudorotaxanes.
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European Journal of Organic Chemistry
10.1002/ejoc.201701374
COMMUNICATION
play a significant role in the host–guest binding process. The
crystal structure clearly confirmed the formation of the
host‒guest system based on pillar[4]arene[1]cis-diepoxy-p-dione
was surrounded by four G1 guest molecules. Totally, the
stoichiometry between H3 and G1 was 1 : 2 in the solid states.
More interestingly, with the assistance of G1 molecules among
the host‒guest system, the crystal showed 2D network in the
solid state. The interactions that help the formation of the 2D
network are also multiple C-H•••π interactions (Figure 3)
between the methylene protons on G1 and the π systems of the
benzene rings, C-H•••O hydrogen bond interactions and C-H•••N
hydrogen bond interactions.
(
H3) and 5-chloropentanenitrile (G1).
(A) H3G1 (Top View)
Figure 3. Wireframe views of the crystal structures indicate the existences of
G1 molecules between the host‒guest complexation H3G1.
(B) H3G1 (Side View)
Figure 2. Ball-stick views of the crystal structure of H3G1. Hydrogen atoms
on H3 have been omitted for clarity. Carbon atoms are red, oxygen atoms are
green, hydrogen atoms are blue, nitrogen atom are black and chlorine atoms
are violet. The guest molecule is blue. The purple dotted lines indicate C-H•••π
interactions and C-H•••O hydrogen bond interactions. C-H•••π interaction
parameters: C-H•••π distance (Å), C-H•••π angle (deg) a, 2.93, 157; b, 3.04,
163; c, 2.90, 160; d, 2.89, 161; f, 3.13, 145; g, 2.81, 167; h, 2.83, 154; C-
H•••O hydrogen bond interaction parameters: C-H•••O distance (Å), C-H•••O
angle (deg) e, 2.86, 134.
Interestingly, to the best of our knowledge, the crystal
structure showed another surprising phenomenon that was not
observed in other single crystals based on pillararenes or
pillararene derivatives. The guest molecules G1 exist among the
host‒guest complexation H3G1 except inclusion in the cavity
of H3. Every G1 molecule outside the rings was surrounded by
four host‒guest systems. Meanwhile, every host‒guest system
Figure 4. Job plot showing the 1 : 1 stoichiometry of the complex between H3
solution using data for Ha of G1. [H3]
and G1 in CDCl
3
0 0
and [G1] are the initial
concentrations of H3 and G1. [H3]
0
+ [G1] = 5.00 mM.
0
Job plot of H3 and G1 was done to further investigate their
complexation stoichiometry and we found they have an 1 : 1
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European Journal of Organic Chemistry
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COMMUNICATION
a
stoichiometry in CDCl
3
solution using data for H of G1 at room
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H O as the oxidation agent and NaHCO as the base at room
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macrocycles such as calixarenes.12 The differences in
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between
hosts
DMpillar[5]arene
(H1),
pillar[4]arene[1]quinone (H2),
pillar[4]arene[1]cis-diepoxy-p-
dione (H3) and guests unsymmetric molecules 5-
chloropentanenitrile (G1) and 5-azidopentanenitrile (G2) were
investigated using NMR titration method. The crystal structure
H3G1 was obtained to prove the complexation between them.
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stoichiometry between H3 and G1 was 1 : 2 in solid state while
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crystal analysis. This work was supported by the Fundamental
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pillar[4]arene[1]cis-diepoxy-p-dione • supramolecular network
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European Journal of Organic Chemistry
10.1002/ejoc.201701374
COMMUNICATION
Entry for the Table of Contents
COMMUNICATION
Pillar[4]arene[1]cis-diepoxy-p-dione
was synthesized under
Supramolecular Chemistry
Chengyou Han,* Shengyi Dong, Dezhi
Zhao, and Daofeng Sun*
environmentally friendly feasible
conditions. X-ray single crystal
analysis between pillar[4]arene[1]cis-
diepoxy-p-dione and 5-
Page No. – Page No.
chloropentanenitrile indicates an 1 :
Mild synthesis of pillar[4]arene[1]cis-
diepoxy-p-dione and guest-assisted
formation of 2D network in solid
state
2
stoichiometry to form 2D
supramolecular network in solid
state.
This article is protected by copyright. All rights reserved.