Quinoxaline-annelated Z-shaped quadruple-bridged orthocyclophanes: Synthesis and crystal structures

Article abstract of DOI:10.1016/j.tet.2010.10.065

A three-step synthesis of nineteen Z-shaped quadruple-bridged [6,6] and [6,4]orthocyclophanes comprising two quinoxaline-based sidewalls are described. The synthesis began from the bis-Diels-Alder adducts B1-B3 followed by ruthenium-promoted oxidation of dichloroetheno-bridges in the adducts to generate a bis-α-diketones, which were then condensed with various arene-1,2-diamines (9a-g) to construct sidewalls (phane parts) of Z-shaped quadruple-bridged orthocyclophanes D1-3, D2g, and D3g. Single-crystal structures of six orthocyclophanes (D1a, D2a, D2f, D3f, D2g-α, and D3g-α) were obtained and revealed that the C_Ar-H?π and π?π stacking interactions between N-containing arene rings are the major driving force for molecular assembly and crystal packing, in addition to the interactions involving the polar OCH₃ groups and the solvate molecules.

Full text of DOI:10.1016/j.tet.2010.10.065

Tetrahedron 67 (2011) 236e249
Contents lists available at ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Quinoxaline-annelated Z-shaped quadruple-bridged orthocyclophanes: synthesis
and crystal structures
Teh-Chang Chou ,*, Kung-Ching Liao b
a,b
a
Department of Applied Chemistry, Chaoyang University of Technology, Wufong, Taichung 41369, Taiwan
Department of Chemistry and Biochemistry, National Chung Cheng University, Minsyong, Chiayi 621, Taiwan
b
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 10 August 2010
Received in revised form 3 October 2010
Accepted 22 October 2010
Available online 1 November 2010
A three-step synthesis of nineteen Z-shaped quadruple-bridged [6,6] and [6,4]orthocyclophanes com-
prising two quinoxaline-based sidewalls are described. The synthesis began from the bis-DielsꢀAlder
adducts B1eB3 followed by ruthenium-promoted oxidation of dichloroetheno-bridges in the adducts to
generate a bis-
construct sidewalls (phane parts) of Z-shaped quadruple-bridged orthocyclophanes D1-3, D2g, and D3g.
Single-crystal structures of six orthocyclophanes (D1a, D2a, D2f, D3f, D2g- , and D3g- ) were obtained
and revealed that the CArꢀH/ and stacking interactions between N-containing arene rings are
the major driving force for molecular assembly and crystal packing, in addition to the interactions in-
volving the polar OCH groups and the solvate molecules.
a-diketones, which were then condensed with various arene-1,2-diamines (9aeg) to
a
a
Keywords:
Cyclophanes
Aza-arenes
Areneearene interaction
Crystal structure
p
p/p
3
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
Recently, we developed an efficient synthetic process for the
0
construction of quinoxaline-based U-shaped multi-bridged [n,n ]
10
Noncovalent intermolecular interactions, such as ion-pairing,
orthocyclophanes having generic structure A. This process consists
hydrogen bonding, and areneearene interactions, play a central
role in manipulating the processes of molecular recognition and
self-assembly to form highly organized structure systems (super-
molecules) of biological and practical importance. The attractive
nonbonded interactions involving aromatic rings (areneearene
of three fundamental operations: (1) using 1,2,3,4-tetrachloro-5,5-
11
dimethoxycyclopentadiene (TDCp, 1) to react with a bis-dien-
ophile, such as cyclohexa-1,4-diene (2), cycloocta-1,5-diene (3), or N-
substituted dioxa-bridged hexahydronaphthalene 4, for the prepa-
ration of a DielseAlder bis-adduct serving as the central scaffold, (2)
1
interactions) comprise
teractions as the major forces that are frequently found in stabi-
p
e
p
stacking, XdH/
p
, and cation/
p
in-
transforming the dichloroetheno-bridges in the bis-adduct to gen-
2
12
erate a bis-a-diketone by ruthenium-promoted oxidation, followed
lizing the base pair stacking in DNA, protein folding, hosteguest
binding, drug receptor interactions, and crystal engineering.
Various prospective applications have been disclosed and in-
spired growing intenseness of synthetic endeavor directed toward
by (3) constructing sidewalls by the condensation of bis-
a
-diketone
3
e5
0
with an arene-1,2-diamine (ADA) to produce [n,n ]orthocyclophanes
embedded with quinoxaline-based aromatic rings. The versatility of
the process is manifested by the presence of two changeable sub-
structures, the intercalator and the quinoxaline ring. The intercalator
originated from the bis-dienophilic cycloalkadiene can serve as the
controller of the size and shape of polycyclic scaffold, and conse-
quently the distance and stereo-alignment between two quinoxaline
rings, the motif of which is derived from various ADA’s. The U- or the
the search for the new arene
p-systems of specially designed ar-
chitecture that may possess specific functions for such applica-
6
tions. In this context, rigid and often symmetric polycarbocyclic
skeletons are frequently utilized to serve as ‘platforms’ for the at-
tachment of functional groups or ligands, which demonstrate the
role of areneearene interactions in long-range electron/energy
0
Z-shape of [n,n ]orthocyclophanes, that is, the syn or anti stereo-
7
8
transfer phenomena, self-assembly, and the formation of the
alignment of two quinoxaline rings, is predestined by the p-facial
hosteguest complexes.9
selectivity of DielseAlder reaction between 1 and cyclic bis-dien-
ophile, which in most cases is well-established and predictable. The
presence of amendable functional groups in the intercalator
would amplify the usefulness of this process. The results of
*
Corresponding author. Tel.: þ886 4 2332 3000x4309; fax: þ886 4 2374 2341;
e-mail address: tcchou@cyut.edu.tw (T.-C. Chou).
0
040-4020/$ e see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.tet.2010.10.065

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
OMe
Cl
237
MeO
Cl
MeO
Cl
OMe
MeO OMe
Cl
Cl
Ar
O
O
NH2
N
Cl
2
H N
O
N
N
N
N
Cl
Cl
1
2
3
ADA
O
4
A
(TDCp)
0
synthesizing the U-shaped multi-bridged [n,n ]orthocyclophanes
A
2. Results and discussion
2.1. Synthesis
10
suggested that the synthetic process appeared to be practical
and prompted us to further exploit the practicability of synthetic
process outlined in Scheme 1 for the synthesis of Z-shaped qua-
0
druple-bridged [n,n ]orthocyclophanes D, utilizing known Diel-
All the bis-adducts B1eB3 were known and readily accessible as
shown in Scheme 2. The endo,anti,endo bis-cycloadduct B1, along
with the easily separable endo,syn,endo bis-cycloadduct B1 , was
seAlder bis-adducts B1eB3. Among them, the benzoquinoxaline-
walled orthocyclophane D1f was previously synthesized as a refer-
ence compound for studying luminescence properties of U-shaped
The newly synthesized Z-
shaped [n,n ]orthocyclophanes D showed luminescence properties
similar to D1f (see Experimental section) and did not disclose dif-
ferent results, when compared with the corresponding U-shaped
n,n ]orthocyclophanes. In this paper we primarily describe the
synthetic implementation and solid-state structures of some Z-
shaped [n,n ]orthocyclophanes, which show areneearene in-
0
obtained from the DielseAlder reaction of cycloocta-1,5-diene (3)
10a
13
quinoxaline-based orthocyclophanes.
with TDCp (1). Bis-adduct B3 could be attained straightforwardly
0
from the DielseAlder reaction of TDCp with naphthalene (8), albeit
ꢁ
under harsh condition (neat, 165 C, 12 days) and in low yield
14
15
(45%). However, bis-adduct B2, a formal bis-adduct of TDCp and
benzene, could only be realized indirectly via the DielseAlder re-
action of TDCp with tricyclic 1,3-cyclohexadiene 7, which was
prepared form the DielseAlder adduct 6 of p-benzoquinone (5) and
0
[
0
16
teractions as the major forces in the crystal packing.
TDCp as shown in Scheme 2. Both bis-adducts B2 and B3 are
Cl
Cl
O
Cl
N
N
Cl
O
Cl
OMe
OMe
OMe
Cl
Cl
Cl
MeO
MeO Cl
MeO
MeO
MeO
MeO
OMe
OMe
OMe
Cl
Cl
Cl
Cl
Cl
Cl
Cl
O
N
B
O
C
N
NH2
NH2
RuCl 3H O (0.11 equiv),
3
4
.
2
D
NaIO (2.5 equiv),
Ru-promoted oxidation
Condensation
Scheme 1. Synthetic strategy for the construction of Z-shaped quinoxaline-based orthocyclophanes D’s.
Cl
MeO
OMe
Cl
Cl
Cl
MeO
Cl
Cl
MeO
Cl
OMe
OMe
+
MeO
Cl
Cl
Cl
Cl
Cl
Cl
OMe
Cl
Cl
B1
B1'
Cl
Cl
Cl
3
MeO OMe
MeO
MeO
Cl
OMe
(ref. 13)
Cl Cl
Cl
Cl
8
OMe
Cl
Cl
Cl
(ref. 14)
Cl
1
Cl
O
O
B3
(TDCp)
5
Cl
O
Cl
MeO
MeO
Cl
Cl
MeO
Cl
Cl
OMe
OMe
MeO
MeO
Cl
Cl Cl
MeO
Cl
Cl
O
(
ref. 15)
(ref. 16)
Cl
Cl
7
Cl
Cl
Cl
6
B2
Scheme 2. Preparation of the DielseAlder bis-adducts B’s.

238
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
B1
B2
B3
B
o
RuCl -3H O (0.11 equiv), NaIO (2.5 equiv), MeCN/H O/CHCl (3:1:3), 0 C
3
2
4
2
3
O
O
O
O
O
O
MeO
OMe
OMe
MeO
MeO
Cl
OMe
OMe
MeO
Cl
Cl
OMe MeO
Cl
Cl Cl
Cl Cl
MeO
Cl
Cl
Cl
C
Cl
OMe
O
O
O
O
O
O
C2 (12 h, 95%)
C3 (12 h, 98%)
C1 (72 h, 84%)
Scheme 3. Synthesis of Z-shaped bis-a-diketones C’s.
chiral and thus were produced as a racemic mixture composed of
The condensation reactions of bis-a-diketones C’s with arene-
equal amount of P- and M-forms. The conversion of bis-adducts B’s
1,2-diamines to achieve the synthesis of Z-shaped quinoxaline-
based orthocyclophanes D’s were next carried out. As shown in
Scheme 4, the condensation reactions were executed by performing
to the corresponding bis-a-diketones C’s essentially followed the
ruthenium-promoted oxidation procedure reported by Khan
12
et al., and the results are summarized in Scheme 3. Thus, when
the reactions of bis-
PhCl (0.04 M) at refluxing temperature and in the presence of
0.10 equiv of Zn(OAc) as a catalyst. Utilizing this condensation re-
a-diketones C’s with 2.20 equiv of ADA’s (9) in
employing RuCl
3
$3H
2
O as promoter (0.11 equiv), NaIO
4
as oxidant
ꢁ
(
2.5 equiv), and stirring at 0 C in the solvent system of CHCl
3
/
2
MeCN/H
provided yellow bis-
2
O (3:3:1) for a period of time, the reactions smoothly
-diketones C1ꢀC3 in good yields. The infrared
spectra showed two strong carbonyl absorption bands at
action procedure, we successfully obtained quadruple-bridged [6,6]
orthocyclophanes D1’s and racemic [6,4]orthocyclophanes D2’s and
D3’s in yields of more than 90% from the reactions of corresponding
a
ꢀ1
1
760ꢀ1800 cm , appropriate to strained cyclic bis-
a
-diketones.
bis-
indicated in Scheme 4, bis-
complete the reactions with ADA’s than bis-
a
-diketones C’s with various 4,5-disubstituted ADA’s, 9aef. As
-diketones C2/C3 took much less time to
-diketone C1. This fact
Due to the poor solubility of C1 in common NMR solvents, only the
a
13
C NMR spectra of C2 and C3 were obtained, each of which con-
a
tained two signals at
dicarbonyl group.
d
185ꢀ189 and supported the presence of
a
-
implies that the nucleophilic addition of ADA’s to the carbonyl
groups occurs on the concave side (anti to the dimethoxymethano
B
B1
B2
B3
o
RuCl -3H O (0.11 equiv), NaIO (2.5 equiv), MeCN/H O/CHCl (3:1:3), 0 C
3
2
4
2
3
O
O
O
O
O
O
MeO
OMe
OMe
MeO
MeO
Cl
OMe
OMe
MeO
Cl
Cl
OMe MeO
Cl
Cl Cl
Cl Cl
C
MeO
Cl
Cl
Cl
Cl
OMe
O
O
O
O
O
O
C2 (12 h, 95%)
C3 (12 h, 98%)
C1 (72 h, 84%)
ADA (2.20 eq), Zn(OAc)2 (0.10 eq), PhCl (0.04 M), reflux
Z
Z
Z
Z
Z
Z
N
N
N
N
N
N
MeO
OMe MeO
Cl
OMe
OMe
MeO
MeO
Cl
OMe
OMe
MeO
Cl
Cl
Cl Cl
Cl Cl
D
MeO
Cl
Cl
Cl
Cl
OMe
N
N
N
N
N
N
Z
Z
Z
Z
Z
Z
D2
D3
D1
a: Z = H
D1a ( 8 h, 94%)
D1b ( 8 h, 94%)
D1c ( 8 h, 92%)
D1d (12 h, 92%)
D1e (NA)
D2a (0.25 h, 92%)
D2b (0.25 h, 94%)
D2c (0.25 h, 94%)
D2d (0.25 h, 93%)
D2e ( 12 h, 89%)
D2f (0.25 h, 93%)
D3a (0.25 h, 99%)
D3b (0.25 h, 95%)
D3c (0.25 h, 91%)
D3d (0.25 h, 98%)
D3e ( 12 h, 93%)
D3f (0.25 h, 95%)
b: Z = Me
c: Z = OMe
d: Z = Cl,
e: Z = NO
2
f: Z = BuD
D1f (10 h, 90%)
Scheme 4. Synthesis of Z-shaped quinoxaline-based orthocyclophanes D’s.

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
239
bridge) of bis-
a
-diketones, in which the saturated intercalator of C1
element and are C
s
-symmetric. In practice, we isolated a major
is more steric demanding due to inward hydrogen atoms. The use of
PhCl as solvent is essential in ensuring a good yield, and in most
cases, the reactions were clean, requiring only filtration and re-
crystallization in handling the reaction product mixtures.
product from the reaction of bis-
81% yield, which displayed a fifteen-line C NMR spectrum and
a-diketone C2 and diamine 9g in
13
1
a
H NMR spectrum containing eight groups of absorptions for
a molecular formula of C30 . The NMR spectral data could
immediately eliminate D2g- to be the product, but could not
discriminate between C -symmetric D2g- and D2g- . Similar
outcome was observed for the reaction of bis- -diketone C3 and
diamine 9g, from which D3g- or D3g- was obtained in 76% yield.
4 6 4
H24Cl N O
The Z-shaped orthocyclophanes synthesized (Scheme 4) exhibit
g
1
13
conformational rigidity and symmetry-reflected H and C NMR
spectra. The quadruple-bridged [6,6]orthocyclophanes D1aef dis-
play NMR spectra reflecting the expected inherent C2v-symmetry.
For example, benzoquinoxaline derivative D1f having molecular
2
a
b
a
a
b
The structural determination for the major product in two cases
1
3
formula C42
H36Cl
4
N
4
O
4
shows a twelve-line C NMR spectrum and
was secured by recourse of X-ray crystallographic analysis and
1
18
a H NMR spectrum containing 10 groups of absorptions. In partic-
ular, a distinct four-proton absorption signal appears at much higher
magnetic field than the other C(sp )eH in the H NMR spectra of
D1aef (e.g., D1a: 0.07 vs 2.71/2.10 and D1f: 0.19 vs 2.72/2.15).
proved to be D2g-a and D3g-a (vide infra).
3
1
2.2. Crystallographic study
d
d
d
d
This signal is ascribed to the methylene protons lying parallel to (on
top of) and most closely to the heteroaromatic ring, as a result of
2.2.1. Molecular structures. Among the synthesized orthocyclo-
phanes shown in Schemes 4 and 5, we obtained single crystals of
17
anisotropic shielding effect, a situation similar to the precursor B1
2.67/2.10/0.80) where anisotropic shielding effect of C]C is op-
erating. On the other hand, the inherent C -symmetry expected for
D1a, D2a, D2f, D3f, D2g-
a, and D3g-a that were suitable for room-
(d
temperature X-ray crystal structure determination by re-
18
2
2 2 3
crystallization from solvent system of EtOH and CH Cl or CHCl .
quadruple-bridged [6,4]orthocyclophanes D2’s and D3’s is evidently
demonstrated by a 13C NMR spectrum containing the number of
absorption line equal to half of the total number of constituent
carbon atoms, and a H NMR spectrum showing matching groups of
absorptions (see Experimental section). It was also noticed that, due
to anisotropic shielding effect, the absorption signals for vinyl pro-
Fig. 1 depicts the molecular structures of D1a, D2a, D2f, D3f, D2g-
a,
and D3g- in the crystal. Their crystal data/structure refinement
a
are compiled in Table 3. All orthocyclophanes assume Z-shaped
geometry, predestined by the stereochemistry of DielseAlder bis-
adducts B1-3, where the phane sidewalls (quinoxaline rings) are
pointed away from each other in antiparallel manner (D1) or helix
mode (D2’s and D3’s). Due to the rigidity of the norbornenyl rings,
the eight-membered ring in D1a is induced to fuse at the junction
1
tons in D2’s (
.79e7.00) shifted upfield comparing, respectively, with the corre-
sponding protons in B2 ( 5.82) and B3 ( 7.07/7.53).
We furthermore subjected an unsymmetrical ADA, pyridine-
,3-diamine (9g), to the condensation reaction with bis- -dike-
d 5.17e5.25) and phenyl protons in D3’s (d 6.80e7.00/
6
ꢁ ꢁ
sites with near-zero torsion angles (5.3 and 1.7 ) and adopts nearly
d
d
ꢁ
19
ideal chair conformation (þ116.8 ) as indicated by the torsion
ꢁ
ꢁ
2
a
angles of 122.6 and 115.6 about the CꢀC bonds that comprise the
arms of the chair and connect norbornenyl rings. On the other
hand, the rigidity of the norbornenyl rings force cyclohexene ring
tones C2 and C3. Due to decomposition of 9g in refluxing chloro-
benzene, which was used as solvent in the preparation of D1-3
(
Scheme 4), toluene was used instead for the synthesis of D2g and
D3g (Scheme 5). In principle, the reaction could yield three ste-
reoisomeric products, D2g- (D3g- ), D2g- (D3g- ), and D2g-
D3g- ), differentiated by the orientation of two nitrogen atoms of
pyridine rings relative to the C]C (benzene ring), as shown in
Scheme 5. Compounds D2g- (D3g- ) and D2g- (D3g- ), in which
the nitrogen atoms of pyridine rings are situated, respectively, at
opposite and same side to the C]C (benzene ring) moiety, are C
symmetric. Compounds D2g- and D3g- have no symmetry
(intercalator) of D2a, D2f, and D2g-a to adopt a conformation with
2
0
great deviations from ideal half-chair form of cyclohexene. The
a
a
b
b
g
double bond is distorted and deviated from planarity with CeC]
ꢁ
ꢁ
ꢁ
(
g
CeC torsion angle of 7.6 , 8.9 , and 7.6 for D2a, D2f, and D2g-
respectively. Likewise, the conformation of benzene-fused cyclo-
hexene ring in D3f and D3g- is greatly deviated from ideal half-
a,
a
a
b
b
a
chair form. The bridged C]C bond of benzocyclohexene ring is
2
-
even more distorted and greatly deviated from planarity with
ꢁ
ꢁ
g
g
CeC]CeC torsion angle of 24.8 and 21.4 for D3f and D3g-a,
O
O
MeO
MeO
Cl
OMe
Condition:
Cl OMe
Cl Cl
N
NH2
9
g (2.20 eq),
NH2
O
O
Zn (OAc) (0.10 eq),
2
9
g
C2/3
PhMe (0.04 M),
reflux, 8 h
N
N
N
N
N
N
N
N
N
MeO
MeO
Cl
OMe
OMe
MeO
MeO
Cl
OMe
OMe
MeO
MeO
Cl
OMe
OMe
Cl Cl
Cl Cl
Cl Cl
Cl
Cl
Cl
N
N
N
N
N
N
N
N
N
D2g-α (81%)
D3g-α (76%)
D2g-β
D3g-β
D2g-γ
D3g-γ
Scheme 5. Reactions of bis-a-diketones C2/C3 with pyridine-2,3-diamine.

240
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
ꢀ
ꢁ
ꢀ
2
(
.49 A (140.9 )] and AreH/Cl close contact [dCl/H (:)¼3.15 A
ꢁ
21,22
108.5 ), Table 2].
D1a employ their solvated quinoxaline ring to connect the nearby,
perpendicularly aligned molecule of D1a chiefly by CArH/ and
OCH interactions, forming a two-dimensional molecular sheet
on ab-plane. The CArH/
As shown in Fig. 2 and Table 1, molecules of
p
3
/p
2
f,g
p
interaction
is endowed with N/H
ꢀ
ꢁ
hydrogen bond [dN/H (:)¼2.73 A (155.0 )] and short C/H dis-
ꢀ
tances (3.12/3.17 A) between two quinoxaline rings, which adopt
2
a,23
edge-to-face herringbone (face-tilted-T) structure
hedral angle of about 70 and a centroid-to-centroid distance of
.57 A. This two-dimensional molecular array of D1a is reinforced
with di-
ꢁ
ꢀ
6
by additional interactions between their polarized methoxy groups
ꢁ
via OCeH/O hydrogen bonds [dO/H (:)¼2.74 (148.7 ) and 2.78
ꢁ
1c,24
(
157.8 )],
bilateral OCH
OCH group in the neighboring molecules of D1a. As indicated in
Fig. 2, the OCH interaction on one side is denoted by the
OCeH/NAr hydrogen bond [dN/H (:)¼2.80 A (131.0 )] and short
and by using the solvated quinoxaline ring to attain
3
/p interactions with the polarized CeH bonds of
3
3
/p
ꢀ
ꢁ
ꢀ
CeH/CAr distances (2.83e4.51 A,
p
-centroid/HeC distance
ꢀ
3
.07 A), and on the other side, by the close contacts of OCeH/NAr
ꢀ
ꢁ
ꢀ
ꢀ
[d
N/H (:)¼3.47 A (107.3 )] and CeH/CAr (3.04e3.82 A,
p-cen-
troid/HeC distance 3.19 A). As shown in Fig. 2 (insert box), binding
of adjacent molecular sheets is attained by means of areneearene
ꢀ
interactions via double CeH/NAr close contacts [dN/H (:)¼2.91 A
ꢁ ꢁ
ꢀ
(
158.7 ), 3.05 A (168.8 )] between solvated and non-solvated qui-
noxaline rings, which are arranged in antiparallel manner and
ꢀ
25
separated by an intercentroid distance of 6.68 A. The association
is secured by a OCH group exerting one OCeH/NAr hydrogen
bond to each of the linked quinoxaline rings [dN/H (:)¼2.62 A
3
ꢀ
ꢁ
ꢀ
ꢁ
(
166.5 ) and 2.80 A (131.0 )].
The -symmetric quadruple-bridged [6,4]orthocyclophane
D2a deposited as a racemic mixture composed of P- and M-forms
from CH Cl /EtOH solution in the orthorhombic space group Pca2
1). Fig. 3a shows the arrangement of molecular aggregates viewed
C
2
2
2
(
along a-axis on bc-plane that are composed of wave-like columns
of D2a molecules. The wave-like molecular column of D2a is con-
structed by means of areneearene interactions between quinoxa-
line rings of adjacent molecules having opposite chirality, which
Fig. 1. ORTEP drawings of the crystal structures. The thermal ellipsoids are drawn at
the 30% level of probability. (a) D1a, (b) D2a, (c) D2f, (d) D3f, (e) D2g- , (f) D3g-
25
assume the parallel-displaced geometry as shown in Fig. 3b
a
a,
(
viewed along c-axis). They are separated by an intercentroid dis-
containing a molecule of solvating CHCl
red, Cl, green.
3
. Color coding: C, gray; H, green; N, blue; O,
ꢀ
ꢁ
tance of 6.48 A with a dihedral angle of about 180 , and linked by
ꢀ
double, nearly linear CeH/NAr hydrogen bonds [dN/H (:)¼2.70 A
ꢁ
ꢀ
ꢁ
(6.7 ) and 2.66 A (5.4 ), Table 1]. This offset parallel structure is
ꢁ
resulting in twisting benzene subunit at fused junction by 8.8 and
further stabilized by OCH
OCH groups of D2a concurrently located close to the quinoxaline
ring of two adjoining molecules of D2a with dH/ distances of
3
/p interactions exerted by the polar
ꢁ
7
.1 , respectively.
3
p
2.2.2. Crystal packing. In the previous study on the crystal packing
ꢀ
ꢀ
ꢀ
2
.54e6.32 A (
p-centroid/HeC distance 4.19 A) and 3.26e7.18 A (p-
of the U-shaped septuple-bridged [7,7]orthocyclophanes (generic
formula A),1 we disclosed that noncovalent interactions relating
the quinoxaline rings with their embedded nitrogen atoms, the
polar methoxy groups at bridging carbons, and the solvating mol-
ecules, are the key driving forces for assembling molecules of this
class to form three-dimensional crystalline architectures in the
crystals. In this section, we describe similar noncovalent in-
teractions observed in controlling the packing of the Z-shaped
orthocyclophanes D’s into two- and three-dimensional structures
in the crystal. Table 1 lists some selected parameters from the X-ray
crystal structures, which describe the structure and packing motifs
involving aryl and methoxy groups. Some selected packing motifs
ꢀ
centroid/HeC distance 5.05 A).
0b
Examination of the crystal packing (Fig. 3a,c, and Table 1) fur-
ther reveals that the binding forces between molecular columns are
3
mainly presented by the polar OCH groups using OCeH/O hy-
ꢀ
ꢁ
ꢀ
ꢁ
drogen bonds [dO/H (:)¼2.57 A (34.5 ), 2.79 A (40.0 )] and
OCH interactions resulting from CeH/NAr and CeH/CAr close
contacts with H/NAr and -centroid/H distances within the
3
/p
p
ꢀ
ꢀ
ranges of 2.9e3.5 A and 3.1e3.8 A, respectively.
The racemic quadruple-bridged [6,4]orthocyclophane D2f co-
crystallized with molecules of CHCl
C2/c. Resembling D2a in molecular skeleton, but annelated by aryl
ring, that is, of more capability for stacking interaction, mol-
3
in the monoclinic space group
pep
in the crystal structures of D1a, D2f, D3f, and D3g-
a having the
ecules of D2f employ two types of areneearene interaction be-
tween benzoquinoxaline rings to construct molecular columns as
illustrated in Fig. 4a. Each molecular column is composed of arrays
of wave-like molecular strips (Fig. 4b). Similar to that used by D2a,
one areneearene interaction adopts offset parallel structure (left,
participation of solvating molecules are outlined in Table 2.
The quadruple-bridged [6,6]orthocyclophane D1a crystallizes
from CH
An examination of the crystal packing of D1a reveals that every
molecule of D1a carries a solvating CH Cl molecule on one of its
two quinoxaline rings by N/HeC hydrogen bond [dN/H (:)¼
2 2
Cl /EtOH solution in the monoclinic space group P2(1)/c.
25
2
2
Fig. 4), in which benzoquinoxaline rings of adjacent molecules of
homochiral D2f are separated by a centriod-to-centriod distance of

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
241
Table 1
a
Selected packing motifs in the crystal structures involving aryl and methoxy groups
Areneearene interaction
OCH
3
/
p
interaction
OMe/OMe
moldb
Shortest interatomic
distance
ArH/NAr H-bond
or close contact
Hydrogen bond or close contact
OCꢀH/NAr
N/H (:)
OCꢀH/(C/N)Ar
C
d
ArꢀH/O
O/H (:)
OCꢀH/O
O/H (:)
c
d
C/N
d
C/C
dN/H (:)
d
d
C/H ()
d
D1a
D2a
D
>
(6.57)
(6.68)
3.59
3.59
2.73 (155.0)
2.91 (158.7)
2.80 (131.0)
3.47 (107.3)
2.62 (166.5)
2.98 (131.7)
3.21 (114.2)
2.83e4.51 (3.07)
3.04e3.82(3.19)
2.74 (148.7)
2.78 (157.8)
3
.05 (168.8)
2.70 (6.7)
.66 (5.4)
> (6.48)
3.65
4.24
2.54e6.32 (4.19)
3.26e7.18 (5.05)
2.98e5.47 (3.77)
2.57 (34.5)
2.79 (40.0)
2
3.48 (86.1)
3
3
.21e5.22 (3.71)
.04e4.42 (3.15)
D2f
> (6.92)
4.08
4.50
3.38
3.45
3.30
3.47
4.15
3.54
3.41
3.58
3.38
3.44
3.15 (176.4)
4.00 (122.7)
3.42 (79.5)
3.40 (85.3)
3.52 (105.6)
3.28 (82.9)
3.11e9.13(5.81)
3.12e7.44(4.55)
2.74e5.80 (3.16)
3.02e6.44 (3.63)
3.16e6.60(4.65)
3.51e6.30 (4.74)
,
(5.27)
, (3.87)
(4.03)
, (4.25)
(3.85)
D3f
2.64 (139.5)
2.66 (138.6)
2.77 (156.5)
2.96 (125.7)
,
D2g-
a
a
3.16 (124.2)
3.52 (127.7)
,
3
3
.54 (78.1)
.37 (89.7)
D3g-
D
(5.85)
3.52
2.62(163.4)
3.32 (99.9)
2.55 (170.5)
3.09 (137.4)
3.30 (126.8)d
3.17e5.91 (4.15)
2.93e5.26 (3.67)
2.76e5.47 (3.62)
2.78e6.17 (4.29)
2.74e6.21 (4.17)
3
.60
3.48
.83
3.93
2.93 (138.8)
2.93 (105.8)
2.78 (125.1)
>
(7.23)
3
2.98 (134.1)d
3.07 (147.2)d
D
(4.88)d
3.89 d
a
ꢀ
ꢁ
Distances (d) are in A unit and angles (:) shown in parentheses are in degree unit ( ).
b
Structure of alignment for arene rings with centroid-to-centroid distance shown in parentheses: (
parallel (parallel-displaced) geometry; (,) face-to-face, parallel, stacking geometry.
The distances of hydrogen atom to all carbon/nitrogen atoms of aryl ring with H-to-centroid distance shown in parentheses.
O) edge-to-face, herringbone (face-tilted-T) geometry; (>) offset
pep
c
d
The interaction involving spacer tetrahydronaphthalene ring of D3f and D3g-a.
Table 2
a,b
Selected packing motifs in the crystal structures involving solvate molecules
Solvate
CleCeH$$$NAr or HeCeCl$$$H
H-bond and close contact
CꢀH$$$NAr
ArꢀH$$$Cl
Cl$$$HꢀCO
CꢀH$$$ClBridgehead
D1a
D2f
CH
CHCl
2
Cl
2
2.49 (140.9)
2.47 (146.7)
3.51 (108.5)
3.12 (134.9)
3
3.06 (111.1)
3.16 ()
3.02 (118.6)
D3f
CHCl
3
2.61 (142.2)
2.98 (161.6)
3.06 (105.4)
3.27 (92.0)
3.28 (116.7)
3.34 (123.9)
3.02 (130.1)
3.32 (137.0)
2.49 (144.5)
3.10 (155.3)
3
3
3
3
.15 (135.3)
.19 (121.8)
.28 (147.9)
.12 (154.5)
D3g-
a
CHCl
3
2.44 (151.1)
.54 (149.3)
3.44 (112.6）
3.27 (136.1)
2.94 (118.3)
3.90 (116.2)
c
2
3.09 (162.9)
a
D2a and D2g-a did not crystallize with solvate molecules.
Distances (d) are in A unit and angles (:) shown in parentheses are in degree unit ( ).
The interaction involving spacer tetrahydronaphthalene ring of D3g-a.
b
c
ꢀ
ꢁ
ꢀ
ꢁ
6
.92 A with dihedral angle of about 180 and are allied by sym-
molecule places its acidic hydrogen atom within the distance range
of forming hydrogen bonds to concurrently link up with electron-
rich nitrogen and chlorine atoms (Fig. 4b). Through collaboration
ꢀ
metrical, double ArH/NAr close contacts [dN/H (:)¼3.15 A
ꢁ
(
176.4 )]. This packing motif is further supported by the OCH
3
/p
ꢀ
ꢀ
close contacts (3.11e9.13 A,
p
-centroid/HeC distance 5.81 A). The
3 3
with the polarized OCH group, CHCl molecules are also re-
other areneearene interaction assumes parallel, face-to-face,
sponsible for stabilizing the association of molecular columns by
26
ꢀ
stacking geometry with a centriod-to-centriod distance of 5.27 A
grabbing nearby homochiral molecules of D2f via OCeH/Cl close
ꢀ
ꢀ
ꢁ
and shortest interplanar carbon-to-carbon distances of 3.54 A be-
contact [dCl/H (:)¼3.02 A (118.6 )]. The association of molecular
tween benzoquinoxaline rings of heterochiral D2f (right, Fig. 4).
columns is also found to be stabilized by the OCH close con-
tacts between D2f of heterochirality (3.12e7.44 A,
troid/HeC distance 4.55 A), Fig. 4a.
3
/p
ꢀ
Interestingly as shown in Fig. 4 and Table 2, the solvating CHCl
3
are
p
-cen-
ꢀ
sited between molecular columns of 2Df and each one of them is
attached to one benzoquinoxaline ring by making use of
Fig. 5 illustrates the packing motifs observed for single crystal of
quadruple-bridged [6,4]orthocyclophane D3f obtained from CHCl
solution in the triclinic space group P1. Bearing benzoquinoxaline
rings similar to D2f, a molecule of D3f operates bilateral connection
with its enantiomeric neighbors to form wave-like molecular strip
ꢀ
ꢁ
Cl
Cl
3
CeH/NAr hydrogen bond [dN/H (:)¼2.47 A (146.7 )], and
CeH/ClBridgehead, CAreH/Cl, and OCeH/Cl close contacts
Cl/H (:)¼3.16 A (129.5 ), dCl/H (:)¼3.12 A (134.9 ), and dCl/H
3
3
ꢀ
ꢁ
ꢀ
ꢁ
[d
ꢀ
ꢁ
(
:)¼3.06 A (111.1 ), respectively]. Worth of notice is that CHCl
3

242
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
different configurations with centriod-to-centriod distances of
ꢀ
ꢀ
4
3
.25 A and 3.85 A, and shortest interplanar distances (dC/N) of
ꢀ
ꢀ
.30 A and 3.47 A, respectively. Both structures of areneearene
interaction are reinforced by the polarized OMe groups via
ꢀ
ꢁ
ꢀ
C
(
AreH/O hydrogen bonds [dO/H (:)¼2.77 A (156.5 ), 2.96 A
ꢁ
125.7 ), Table 1]. Alliance between molecular strips is mainly
ꢀ
endowed with OCH
troid/HeC distance 4.65 A; 3.51e6.30 A,
3
/p
close contacts (3.16e6.60 A,
p
-cen-
ꢀ
ꢀ
p
-centroid/HeC dis-
tance 4.74 A). Interestingly, in this alliance a bridgehead chlorine
ꢀ
atom is very near to the cyclohexene ring (intercalator) of adjacent
ꢀ
D2g-
(
a
to express ]CeH/Cl hydrogen bonds [dCl/H (:)¼2.93 A
ꢁ
ꢀ
ꢁ
116.5 )/2.99 A (117.1 )], further locking molecular strips together,
Fig. 6.
The quadruple-bridged [6,4]orthocyclophane D3g-
lized with molecules of CHCl in the monoclinic space group P2(1)/
c. Although having pyridopyrazine-ring sidewalls as D2g- , the
crystal of D3g- interactions, in-
employs the mode of CArꢀH/
stead of stacking interactions, for associating molecules of
D3g- . Fig. 7a depicts enantiomeric pairs of D2g- aligning to form
molecular arrays viewed along c-axis, which clearly show their
association with the assist of CArꢀH/ interactions by means of
double N/H close contacts [dN/H (:)¼2.55 A (170.5 )/3.09 A
a
co-crystal-
3
a
a
p
pep
Fig. 2. The packing motifs observed for crystal D1a viewed along c-axis on ab-plane,
showing molecular sheet assembled mainly by using the motifs of CArꢀH/ and
OCH interactions. Insert shows double H/N hydrogen bonds (cyan dotted line)
a
a
p
3
/p
p
connecting two molecules of D1a in adjacent molecular sheets. In this and successive
figures, unless otherwise specified, the packing motifs are denoted by symbol and color
as following: white double-headed arrow for arene-arene interaction, yellow double-
ꢀ
ꢁ
ꢀ
ꢁ
ꢀ
(137.4 )] with a centriod-to-centriod distance of 7.32 A between
pyridopyrazine rings, and is reinforced by OCH interactions
-centroid/HeC distance 4.29 A with OCH/N hy-
headed arrow for OCH
3
/
p
interaction, cyan dotted line for CArꢀH/NAr, OCꢀH/NAr
,
3
/p
and ClCꢀH/NAr, yellow dotted line for CArꢀH/O and OCꢀH/O, and green dotted line
for CArꢀH/Cl, OCꢀH/Cl, and CꢀH/ClBridgehead hydrogen bond or close contact. Color
coding for atom: C, gray; H, white; N, blue; O, red; Cl, green. Distances (d) and angles
ꢀ
ꢀ
[2.78e6.17 A,
p
ꢀ
ꢁ
ꢀ
drogen bond (dN/H (:)¼2.78 A (125.1 )); 2.74e6.21 A,
p
-cen-
ꢀ
(
:) are listed in Tables 1 and 2.
troid/HeC distance 4.17 A] and CAreH/O close contacts [dN/H
ꢀ
ꢁ
(
:)¼3.07 A (147.2 )] between the methoxyl oxygen atom and
a hydrogen atom of fused-benzene rings (intercalator), as shown in
Fig. 7b. The molecular array of D3g- is constructed predominantly
interaction between two pyr-
idopyrazine rings and the fused-benzene rings of intercalator,
separated by centriod-to-centriod distances of 5.85 ꢀA , 4.88 ꢀA , and
in the crystal, taking advantage of direct
p
ep
interaction between
a
benzoquinoxaline rings in face-to-face, parallel-stacked structure.
Both structures of areneearene interaction are reinforced by the
polarized OMe groups via CAreH/O hydrogen bonds [dO/H (:)¼
by a three-component CArꢀH/
p
ꢀ
ꢁ
ꢀ
ꢁ
ꢀ
2
.64 A (139.5 ), 2.66 A (138.6 )]. Interestingly, the configuration of
4.57 A, respectively (Fig. 7b, Table 1). Pyridopyrazine rings are
p
e
p
stacked interactions at the two sides are different in the
connected using interactions of double N/H close contacts [d
N/H
ꢀ
ꢀ
ꢀ
ꢁ
ꢀ
ꢁ
centriod-to-centriod distance (3.87A vs 4.03 A), the shortest
interplanar distance (dC/N: 3.38 A vs 3.45 A), and the striking
feature of solvation. As shown in Fig. 5b (left), the solvating CHCl
molecules discriminatingly bind only one of the two benzoqui-
noxaline rings in D2f by tripodal style using CeH/NAr hydrogen
(:)¼2.62 A (163.4 )/3.32 A (99.9 )], while intermolecular in-
ꢀ
ꢀ
teraction between pyridopyrazine and fused-benzene rings is
presented by N/H close contact [dN/H (:)¼3.30 ꢀA (126.8 )]. In
ꢁ
3
this packing motif, OMe groups are located close to pyridopyrazine
interactions[2.93e5.26 ꢀA ,
distance 3.67 A, with OCH/N hydrogen bond (d
ring to apply OCH /
3
p
p
-centroid/HeC
ꢀ
ꢁ
ꢀ
ꢁ
ꢀ
ꢀ
bonds [dN/H (:)¼2.49 A (144.5 ), 2.61 A (142.2 )], and two
(:)¼2.93 A
N/H
ꢀ
ꢁ
ꢀ
ꢁ
ꢀ
ꢀ
C
AreH/Cl close contacts [dCl/H (:)¼2.98 A (161.1 )/3.32 A
(105.8 )); 3.17e5.91 A,
p-centroid/HeC distance 4.15 A], and the
ꢁ
ꢀ
ꢁ
ꢀ
ꢁ
(
137.0 ), 3.10 A (155.3 )/3.15 A (135.3 )]. The molecule of CHCl
3
is
fused-benzene ring to exert C eH/O hydrogen bond [d
(:)¼
Ar
O/H
2.98 ꢀA (134.1 )], further sustain the structure. Examination of
ꢁ
thus positioned and oriented such that its hydrogen atom is also
brought into closely contact with the bridgehead chlorine atom of
crystal packing reveals that the solvate molecule of CHCl appears
3
ꢀ
ꢁ
ꢀ
ꢁ
1b,24
D3f [dCl/H (:)¼3.02 A (130.1 ), 3.34 A (123.9 )].
affixed benzoquinoxaline rings then assemble to form a ‘dimer’ of
D2f via stacking interactions. Furthermore, the solvating
CHCl appear to play a key role in sustaining the association of
molecular strips of D3f, as close contacts with nearby molecules of
Two CHCl
3
-
to be entrapped in the cavity formed by four molecules of D3g-
a
(Fig. 7c and Table 2), and to act as binding agent for connecting
pe
p
adjacent molecular arrays to construct 3D-network of crystal
structure.
3
ꢀ
ꢁ
ꢀ
D3f by motifs of CAreH/Cl [dCl/H (:)¼3.28 A (147.9 ), 3.12 A
3. Conclusion
ꢁ
ꢀ
ꢁ
ꢀ
ꢁ
(
3
154.5 )] and OCeH/Cl [dCl/H (:)¼3.06 A (105.4 ), 3.27 A (92.0 ),
ꢀ
ꢁ
0
.28 A (116.7 )] were observed as well, as shown in Fig. 5b (right).
In summary, we have synthesized multi-bridged [n,n ]orthocy-
Additional forces of supporting association of molecular strips de-
rived from the interactions of the polarized OMe groups with
benzoquinoxaline via the OCH
centroid/HeC distance 3.16 A; 3.02e6.44 A,
clophanes encompassing two sidewalls (phane parts) oriented in
opposite direction and made of quinoxaline, 6,7-disubstituted
quinoxaline, benzoquinoxaline or pyrido[2,3-b]pyrazine rings by
a three-step synthetic route outlined in Scheme 1. The synthesis
starts with three bis-DielseAlder adducts and subsequently in-
volves the ruthenium-promoted oxidation and condensation of the
ꢀ
3
/
p
close contacts (2.74e5.80 A,
p
-
ꢀ
ꢀ
p
-centroid/HeC
ꢀ
distance 3.63 A) and fused-benzene rings (intercalator) via
ꢀ
ꢁ
C
AreH/O hydrogen bonding [dO/H (:)¼2.94 A (156.1 )], Fig. 5a.
The packing motifs observed for crystal of pyridopyrazine ring-
resulting bis-a-diketones with various arene-1,2-diamines to fur-
walled quadruple-bridged [6,4]orthocyclophane D2g-
clinic space group P2(1)/c) is shown in Fig. 6. The association of
D2g- to form wave-like molecular strips is predominantly ach-
ieved by interactions between parallel-stacked pyridopyr-
azine rings. Similar to those observed in the crystal of D3f, the
stacking interactions in the crystal of D2g- also adopt two
a
(mono-
nish nineteen Z-shaped quadruple-bridged [6,6] and [6,4]ortho-
cyclophanes, demonstrating the versatility and efficacy of the
synthetic method. Among the synthesized orthocyclophanes we
a
pep
obtained single crystals of D1a, D2a, D2f, D3f, D2g-
and examined their crystal structure and packing. Areneearene
interactions between N-containing arene rings, in modes of
a, and D3g-
pe
p
a
a

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
243
Fig. 3. The packing motifs observed for crystal D2a. (a) view along a-axis showing the alignment of molecular columns on bc-plane (b) view along c-axis showing the packing motifs
of assembling a wave-like molecular column on ab-plane. (c) view along b-axis showing the packing motifs of binding between molecular columns on ca-plane.
C
ArꢀH/
allel-displaced geometry (D1a, D2a, D2f, and D3g-
face, stacking interaction (D2f, D3f, and D2g-
served as the major driving force for molecular assembly and
interaction, ni-
p
interaction with face-tilted-T (D1a and D3g-
) and face-to-
), were ob-
a
) or par-
combination, these results suggest that design and synthesis of
quinoxaline-based multi-bridged orthocyclophanes that have po-
tential of building up complex crystalline architectures taking ad-
vantage of these noncovalent interactions could be realized by
synthetic strategy shown in Scheme 1.
a
p
e
p
a
crystal packing. In the packing motif of CArꢀH/
p
trogen atoms at heteroaromatic ring often play significant role
through arrangement of double ArH/NAr hydrogen bonding or
close contact. Additional noncovalent interactions involving the
4. Experimental section
CꢀH bond or oxygen atom of polar OCH
3
group and the solvate
CHCl molecule with its acidic H and high electronegative Cl, which
4.1. General (see Supplementary data)
3
are attributed cooperatively to the formation of three-dimensional
crystalline architectures in the crystals, were also disclosed. In
4.1.1. General procedure for the preparation of bis-
a-diketones C. A
suspension of NaIO (2.50 mmol) and RuCl $3H O (0.11 mmol) in
4
3
2

244
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
Fig. 4. The packing motifs observed for crystal D2f with solvating CHCl
molecular columns is mediated by solvating molecules. (b) The middle molecular column shown in (a) is viewed along a-axis on bc-plane to show the association of molecules of
D2f by the parallel-displaced interaction, and the parallel-stacked interaction.
3
. (a) The arrangement of molecular columns on ab-plane viewed along c-axis. The association between
p
ep
pep
water (3.4 mL) was added in portions to an ice-cooled suspension of
9-ene-5,6,13,14-tetraone (C2). Reaction time 12 h, yield 95%. Mp
13
15
14
ꢁ
bis-DA-adduct B1, B2, or B3 (1.0 mmol) in CHCl
CH CN (10 mL) over a period of hours, monitored by TLC and H
NMR. After the reaction was completed, the mixture was added
water (50 mL) and extracted with CHCl
(2ꢂ15 mL). The combined
organic phase was washed with water (2ꢂ20 mL), dried over MgSO
and evaporated. Purification by recrystallization from CHCl affor-
ded yellow platelets of bis- -diketone C. In some cases, the reaction
mixture was filtered directly to give a residue, which was washed
with CH
CN (2ꢂ30 mL) and purified via recrystallization.
3
(10 mL) and
295e298 C (decomp.); IR (KBr) 3003 (m), 2954 (s), 2845 (m),
1
ꢀ1
1
3
1810 (s), 1793 (s), 1771 (s), 1456 (s), 1216 cm
(400 MHz, CDCl
5.74 (d, J¼1.0 Hz, 2H), 3.76 (s, 6H), 3.54 (s,
6H), 3.13 (d, J¼5.6 Hz, 2H), 3.03 (d, J¼5.6 Hz, 2H); C NMR
(100 MHz, CDCl 188.3 (s), 186.2 (s), 124.7 (d), 101.9 (s), 78.8 (s),
78.6 (s), 52.9 (q), 52.3 (q), 39.9 (d), 36.0 (d); MS (FAB) 529 (w)
(s); H NMR
3
) d
13
3
4
,
3
) d
3
þ
þ
a
[Mþ5] , 527 (w) [Mþ3] , 154 (100). Anal. Calcd for C20
4 8
H18Cl O
(528.16): C, 45.48; H, 3.44; O, 24.23; found: C, 45.42; H, 3.34; O,
24.52.
3
4
.1.1.1. (1 ,2 ,5 ,6 ,9 ,10 ,13 ,14 )-1,6,9,14-Tetrachloro-
a
b
a
b
b
a
b
a
4.1.1.3. (1a,2b,3a,4b,7b,8a,15b,16a)-1,4,7,16-Tetrachloro-
19,19,20,20-tetramethoxyhexacyclo [14.2.1.1 .0 .0 .0 ]icosane-
6
,9 2,13 5,10
4,7 2,15 3,8 9,14
1
7,17,18,18-tetramethoxypentacyclo [12.2.1.1 .0 .0 ]octadecane-
7
2
,8,15,16-tetraone (C1). Reaction time 72 h, yield 84%. Mp
9(14),10,12-triene-5,6,17,18-tetraone (C3). Reaction time 12 h, yield
ꢁ
ꢁ
94e296 C (decomp.); IR (KBr) 2991 (m), 2951 (m), 2905 (m), 2847
98%. Mp 287e288 C (decomp.); IR (KBr) 2995 (w), 2954 (m), 2848
ꢀ
1
1
ꢀ1
1
(
m), 1794 (s), 1766 (s), 1468 (s), 1287 cm (s); H NMR (400 MHz,
(m), 1802 (s), 1770 (s), 1466 (m), 1230 cm (s); H NMR (400 MHz,
CDCl
7.54 (dd, J¼6.4, 3.5 Hz, 2H), 7.29 (dd, J¼6.4, 3.5 Hz, 2H), 3.81
(s, 6H), 3.79 (d, J¼12.5 Hz, 2H), 3.53 (s, 6H), 3.52 (d, J¼12.5 Hz, 2H);
CDCl
3
)
d
3.69 (s, 6H), 3.52 (s, 6H), 2.82 (d, J¼10.2 Hz, 4H), 2.08 (d,
3
) d
þ
J¼11.6 Hz, 4H), 0.76 (m, 4H); MS (FAB) 564 (3) [Mþ8] , 556 (7)
þ
13
[M] ; 154 (100). Anal. Calcd for C22
H24Cl
4
O
8
(558.23): C, 47.33; H,
3
C NMR (100 MHz, CDCl ) d 188.6 (s), 185.1 (s), 129.7 (d), 128.5 (d),
4
.33; O, 22.93; found: C, 47.23; H, 4.66; O, 22.53.
126.8 (s), 101.8 (s), 80.9 (s), 79.0 (s), 52.9 (q), 52.4 (q), 42.1 (d), 36.9
þ
þ
(
d); MS (FAB) 579 (2) [Mþ5] , 577 (1) [Mþ3] , 154 (100). Anal.
Calcd for C24 (578.22): C, 49.85; H, 3.49; O, 22.14; found: C,
49.60; H, 3.51; O, 22.34.
4
.1.1.2. (1
a
,2
b
,3
a
,4
b
,7
b
,8
a
,11
b
,12
a
)-1,4,7,12-Tetrachloro-
4 8
H20Cl O
4
,7 2,11 3,8
15,15,16,16-tetramethoxypentacyclo [10.2.1.1 .0 .0 ]hexadecane-

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
245
Fig. 5. The packing motifs observed for crystal D3f with solvating CHCl
cule of D3f operates bilateral connection to form molecular array with its enantiomers
using two face-to-face, parallel-stacked interactions having different centriod-to-
centriod distances and status of salvation. Inter-array association is attained mainly by
OCH close contacts. (b) The face-to-face, parallel-stacked interaction be-
tween pairs of CHCl -attached benzoquinoxaline rings showing the involvement of
molecule of CHCl intermolecular association. The benzene ring of spacer tetrahy-
dronaphthalene in D3f is cyan colored.
3
. (a) A mole-
pep
Fig. 7. The packing motifs observed for crystal D3g-
sections of two molecular arrays, each formed by enantiomeric pair on ab-plane
a
and solvating CHCl
3
. (a) Cross
3
/
p
pep
viewed along c-axis. (b) Molecular arrays on ac-plane viewed along b-axis by rotating
3
ꢁ
(
a) 90 . (c) The formation of CHCl
3
@D3g-
a
, in which the CHCl
3
molecule entrapped in
3
the cavity formed by four molecules of D3g-a.
J¼11.6 Hz, 4H), 0.07 (dd, J¼10.2, 9.6 Hz, 4H); 13C NMR (100 MHz,
4
.1.2. General procedure for the preparation of symmetric bis-qui-
CDCl
3
)
d
152.6 (s),142.4 (s),129.8 (d),129.4 (d),110.3 (s), 75.9 (s), 52.3
noxalines C. Into a solution of bis- -diketone C (0.50 mmol) in
chlorobenzene (12.5 mL) containing a catalytic amount of zinc ac-
etate was added o-phenylenediamine (1.10 mmol) under reflux for
hours, monitored by TLC and H NMR. The reaction mixture was
filtered to remove salt and the filtrate was concentrated. The resi-
3
due was purified via recrystallization from EtOH/CHCl (3/2 by vol)
a
þ
(
[
q), 51.9 (q), 49.5 (d), 22.1 (t); MS (FAB) 707 (8) [MþHþ6] , 705 (22)
þ
þ
þ
MþHþ4] , 703(42) [MþHþ2] , 701(31) [MþH] ,154(100); UV/vis
ꢀ1
3
ꢀ1
1
(CHCl
3
)
)
l
abs
(e
) 244, 318, 330 nm (70,453 mol dm cm ). Emission
(CHCl
3
l
em 390 nm. Anal. Calcd for C34 : C, 58.13; H, 4.59;
4 4 4
H32Cl N O
N, 7.98; O, 9.11; found: C, 58.22; H, 4.49; N, 7.92; O, 9.10.
to afford pure adduct.
4
.1.2.2. (1 ,2 ,5 ,6 ,17 ,18 ,21 ,22 )-8,15,24,31-Tetraaza-
a
b
a
b
b
a
b
a
1
,6,17,22-tetrachloro-33,33,34,34-tetramethoxy-11,12,27,28-tetrame-
4
.1.2.1. (1
a,2b,5a,6b,17b,18a,21b,22a)-8,15,24,31-Tetraaza-
16,17 2,21 5,18 7,10 9,14 23,32 25,30
thylnonacyclo[20.10.1.1.
triacontane-7(10),8,10,12,14,23(32),24,26,28,30-decaene
.0 .0 .0 .0 .0
.0
]tetra-
1
,6,17,22-tetrachloro-33,33,34,34- tetramethoxynonacyclo[20.10.1.1.
1
6,17 2, 21 5 ,18 7 ,10 9,14 23, 32 2 5, 30
.
0
.0
.0
.0
.0
.0
]tetratriacontane-7
ꢁ
(D1b). Reaction time 8 h, yield 94%. Mp>300 C; IR (KBr) 2983 (w),
(
10),8,10,12,14,23(32),24,26,28,30-decaene (D1a). Reaction time 8 h,
yield 94%. Mp 318e321 C (decomp.); IR (KBr) 3089 (w), 2942 (s),
926 (s), 2902 (m), 2839 (m), 1511 (s), 1463 (s), 1199 cm (s); H
NMR (400 MHz, CDCl
8.23 (dd, J¼6.2, 3.4 Hz, 4H), 7.81 (dd, J¼6.2,
.4 Hz, 4H), 3.63 (s, 6H), 3.34 (s, 6H), 2.71 (d, J¼10.2 Hz, 4H), 2.10 (d,
ꢀ
1
1
ꢁ
2949 (s), 2839 (m),1499 (s),1194 cm (s); H NMR (400 MHz, CDCl
d
3
)
ꢀ
1
1
7.98 (s, 4H), 3.61 (s, 6H), 3.33 (s, 6H), 2.65 (d, J¼10.2 Hz, 4H), 2.51 (s,
2
13
1
(
7
2H), 2.06 (d, J¼11.6 Hz, 4H), 0.02 (dd, J¼10.2, 9.6 Hz, 4H); C NMR
100 MHz, CDCl 151.6 (s), 141.0 (s), 140.3 (s), 128.6 (d), 110.3 (s),
5.9 (s), 52.2 (q), 51.8 (q), 49.6 (d), 22.1 (t), 20.3 (q); MS (FAB) 764 (1)
3
) d
3
) d
3
þ
þ
þ
þ
[
[
(
Mþ8] , 762 (2) [Mþ6] , 760 (6) [Mþ4] , 758 (7) [Mþ2] , 756 (2)
þ
M] , 154 (100); UV/vis (CHCl
3
):
l
abs
(
e
) 253, 328, 343 nm
ꢀ
1
3
ꢀ1
65,574 mol dm cm ). Emission(CHCl
3
)
l
em 380 nm. HRMS(FAB)
þ
calcd for C38
H
41Cl
4
N
4
O
4
[MþH] : 757.1882; found: 757.1889.
4
.1.2.3. (1
a,2b,5a,6b,17b,18a,21b,22a)-8,15,24,31-Tetraaza-
1
,6,17,22-tetrachloro-11,12,27,28, 33,33,34,34-octamethoxynonacyclo
1
6,17 2,21 5,18 7,10 9,14 23,32 25,30
[
(
20.10.1.1.
.0 .0 .0 .0 .0
.0
]tetratriacontane-7
10),8,10,12,14,23(32),24,26,28,30-decaene (D1c). Reaction time 8 h,
ꢁ
yield 92%. Mp>300 C; IR (KBr) 2948 (s), 2844 (m), 1631 (m), 1504
ꢀ1
1
(
s), 1469 (s), 1430 (s), 1244 cm (s); H NMR (400 MHz, CDCl
7.54 (s, 4H), 4.06 (s, 12H), 3.61 (s, 6H), 3.33 (s, 6H), 2.67 (d,
J¼10.2 Hz, 4H), 2.07 (d, J¼11.6 Hz, 4H), 0.04 (dd, J¼10.2, 9.6 Hz, 4H);
3
)
d
13
Fig. 6. The packing motifs observed for crystal D2g-
a
showing two molecular bands
C NMR (100 MHz, CDCl
3
) d 152.3 (s), 149.9 (s), 139.1 (s), 110.7 (s),
formed by two types of
p
e
p
interaction between parallel-stacked pyridopyrazine rings
107.5 (d), 76.0 (s), 56.5 (q), 52.2 (q), 51.8 (q), 49.8 (d), 22.1 (t); MS
ꢀ
with (a) a centriod-to-centriod distance of 4.25 A and (b) a centriod-to-centriod dis-
þ
þ
þ
(
FAB) 828 (5) [Mþ8] , 826 (18) [Mþ6] , 824 (26) [Mþ4] , 822 (29)
ꢀ
tance of 3.85 A. Alliance between molecular bands is mainly endowed with OCH
3
/
p
þ
þ
ꢁ
ꢀ
[Mþ2] , 820 (7) [M] , 64 (100); UV/vis (CHCl
3
abs
) l (e
) 248, 359 nm
interaction and ]CeH/Cl hydrogen bonds [dCl/H (:)¼2.93 ꢀ
A
(116.5 )/2.99 A
ꢀ
1
3
ꢀ1
ꢁ
117.1 )], cyan dotted arrow].
(28,145 mol dm cm ). Emission (CHCl
)
lem 381 nm. HRMS
(
3

246
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
þ
(
FAB) calcd for C38
H
H
41Cl
40Cl
4
N
4
O
8
[MþH] : 821.1653; found: 821.1666.
727.1419. Anal. Calcd for C36
O, 8.78; found: C, 59.19; H, 4.77; N, 7.67; O, 8.76.
4 4 4
H34Cl N O : C, 59.35; H, 4.70; N, 7.69;
Anal. Calcd for C38
4
N
4
O
8
: C, 55.49; H, 4.90; N, 6.81; O, 15.56;
found: C, 55.39; H, 4.69; N, 6.73; O, 15.38.
4
.1.2.8. (1
a
,2
b
,3
a
,4
b
,15
b
,16
a
,19
b,20a)-6,13,22,29-Tetraaza-
4
.1.2.4. (1
a,2b,5a,6b,17b,18a,21b,22a)-8,15,24,31-Tetraaza-
1,4,15,20-tetrachloro-9,10,25,26,31,
31,32,32-octamethoxynoncyclo
1
4,15 2,19 3,16 5,14
.07,12.0
21,30 23,28
1
[
(
1
2
,6,11,12,17,22,27,28-octachloro-33,33,34,34-tetramethoxynonacyclo
[18.10.1.1.
.0
.0
.0
.0
]dotriacontane-5
20.10.1.1.1 .0 .0 .0 .0 .0
6,17
2,21 5,18 7,10 9,14 23,32 25,30
.0
]tetratria-contane-7
(14),6,8,10,12,17,21(30),22,24,26,28-undecaene (D2c). Reaction time
ꢁ
10),8,10,12,14,23(32),24,26,28,30-decaene (D1d). Reaction time
2 h, yield 92%. Mp>300 C; IR (KBr) 3078 (w), 3065 (w), 3006 (m),
15 min, yield 94%. Mp>300 C; IR (KBr) 2995 (m), 2948 (s), 2844
ꢁ
ꢀ1
1
(m), 1631 (m), 1504 (s), 1469 (s), 1429 (s), 1243 cm (s); H NMR
(400 MHz, CDCl 7.55 (s, 2H), 7.46 (s, 2H), 5.19 (s, 2H), 4.07 (s, 6H),
4.01 (s, 6H), 3.78 (s, 6H), 3.37 (s, 6H), 3.36 (d, J¼10.1 Hz, 2H), 2.42 (d,
ꢀ1
1
984 (m), 2949 (s), 2907 (m), 2842 (m), 1481 (s), 1197 cm (s); H
8.34 (s, 4H), 3.63 (s, 6H), 3.34 (s, 6H), 2.71
3
) d
3
NMR (400 MHz, CDCl ) d
13
(
4
(
(
(
d, J¼10.2 Hz, 4H), 2.08 (d, J¼11.6 Hz, 4H), 0.02 (dd, J¼10.2, 9.6 Hz,
J¼10.1 Hz, 2H); C NMR (100 MHz, CDCl
3
) d 152.5 (s), 152.4 (s),
13
H); C NMR (100 MHz, CDCl
3
)
d
153.8 (s), 141.0 (s), 134.5 (s), 130.1
149.8 (s), 149.0 (s), 139.5 (d), 139.2 (d), 124.3 (d), 111.1 (s), 107.6 (s),
107.5 (s), 75.9 (s), 75.0 (s), 56.4 (q), 56.4 (q), 52.3 (q), 52.1 (q), 43.8
d), 110.2 (s), 75.8 (s), 52.4 (q), 52.0 (q), 49.5 (d), 22.1 (t); UV/vis
CHCl
CHCl
ꢀ
1
3
ꢀ1
þ
þ
3
)
)
l
abs
(
e
) 249, 344 nm (63,425 mol dm cm ). Emission
(d), 38.4 (d); MS (FAB) 796 (2) [Mþ6] , 790 (2) [M] , 154 (100); UV/
ꢀ1 3
ꢀ1
3
l
em 391 nm. Anal. Calcd for C34 : C, 48.60; H,
H28Cl
8
N
4
O
4
vis (CHCl
(CHCl
91.1209; found: 791.1215. Anal. Calcd for C36
3
)
l
abs
(
e) 250, 361 nm (43,856 mol dm cm ). Emission
þ
3
.36; N, 6.67; O, 7.62; found: C, 48.40; H, 3.60; N, 6.72; O, 7.98.
3
)
lem 381 nm. HRMS (FAB) calcd for C36
H
35Cl
4
N
4
O
8
[MþH] :
7
H34Cl
4
N
4
O
8
(794.51):
4
.1.2.5. (1
a
,2
b
,5
a
,6
b
,21
b
,22
a
,25
b
,26
a
)-8,19,28,38-Tetraaza-
C, 54.56; H, 4.32; N, 7.07; O, 16.15; found: C, 54.28; H, 4.34; N, 7.14;
O, 16.32.
1
[
,6,21,26-tetrachloro-1,41,42,42-tetramethoxyundecacyclo
24.14.1.16 .0
,21
2,25 5,22 7,20 9,18 11,16 27,40 29,38 31,36
.0
.0
.0
.0
.0
.0
.0
]dote-
tracontane-7(20), 8,10,12,14,16,18,27(40),28,30,32,34,36-tetra-deca-
4.1.2.9. (1
a,2b,3a,4b,15b,16a,19b,20a)-6,13,22,29-Tetraaza-
ꢁ
ene (D1f). Reaction time 10 h, yield 90%. Mp>300 C; IR (KBr) 3056
1,4,9,10,15,20,25,26-hexachloro-31, 31,32,32-tetramethoxynoncyclo
ꢀ
1
14,15 2,19 3,16 5,14
.07,12.0
21,30 23,28
(
(
4
w), 2981 (m), 2947 (m), 2843 (m), 1551 (m), 1456 (m), 1189 cm
[18.10.1.1.
.0
.0
.0
.0
]dotriacontane-5
1
s); H NMR (400 MHz, CDCl
H), 7.64 (dd, J¼6.4, 3.5 Hz, 4H), 3.61 (s, 6H), 3.37 (s, 6H), 2.72 (d,
J¼10.2 Hz, 4H), 2.15 (d, J¼11.6 Hz, 4H), 0.19 (dd, J¼10.2, 9.6 Hz, 4H);
3
)
d
8.79 (s, 4H), 8.14 (dd, J¼6.4, 3.5 Hz,
(14),6,8,10,12,17, 21(30),22,24,26,28-undecaene (D2d). Reaction
time 15 min, yield 93%. Mp>300 C; IR (KBr) 3082 (w), 2982 (m),
ꢁ
ꢀ1
1
2950 (s), 2845 (m), 1474 (s), 1194 cm (s); H NMR (400 MHz,
CDCl
8.37 (s, 2H), 8.27 (s, 2H), 5.19 (d, J¼1.1 Hz, 2H), 3.80 (s, 6H),
3.37 (s, 6H), 3.35 (d, J¼10.1 Hz, 2H), 2.44 (dd, J¼10.1, 1.1 Hz, 2H);
NMR (100 MHz, CDCl 153.6 (s), 152.9 (s), 141.2 (s), 141.0 (s), 134.8
1
3
C NMR (100 MHz, CDCl
3
)
d
153.3 (s), 138.7 (s), 133.4 (s), 128.3 (d),
3
) d
13
1
27.8 (d), 127.0 (d), 109.2 (s), 75.8 (s), 52.2 (q), 51.8 (q), 49.3 (d), 22.1
C
þ
þ
(
[
(
t); MS (FAB) 807 (3) [MþHþ6] , 805 (8) [MþHþ4] , 803 (7)
3
) d
þ
MþHþ2] , 154 (100); UV/vis (CHCl
3
)
l
abs
(
e
) 279, 350, 367 nm
(s), 134.7 (s), 130.1 (d, 2C), 124.3 (d), 110.5 (s), 75.5 (s), 74.6 (s), 52.5
ꢀ
1
3
ꢀ1
þ
151,873 mol dm cm ). Emission (CHCl
: C, 62.85; H, 4.52; N, 6.98; O, 7.97; found:
C, 62.81; H, 4.72; N, 7.14; O, 7.81.
3
)
lem 479 nm. Anal.
(q), 52.3 (q), 43.3 (d), 38.1 (d); MS (FAB) 813 (4) [Mþ8] , 811 (5)
þ
þ
þ
Calcd for C42
H36Cl
4
N
4
O
4
[Mþ6] , 809 (4) [Mþ4] , 807 (3) [Mþ2] , 154 (100); UV/vis (CHCl
3
)
ꢀ
1
3
ꢀ1
l
abs
(
e) 249, 344 nm (67,546 mol dm cm ). Emission (CHCl
3
)
l
em
þ
3
91 nm. HRMS (FAB) calcd for C32
found: 806.9229. Anal. Calcd for C32
H
H
23Cl
8
N
4
O
4
[MþH] : 806.9228;
4
.1.2.6. (1
a
,2
b
,3
a
,4
b
,15
b
,16
a
,19
b
,20
a
)-6,13,22,29-Tetraaza-
22Cl
8
N
4
O
4
: C, 47.44; H, 2.74; N,
1
,4,15,20-tetrachloro-31,31,32,32-tetramethoxynoncyclo
6.92; O, 7.90; found: C, 47.48; H, 2.43; N, 7.05; O, 8.02.
18.10.1.1.1
4,15
.0
2,19 3,16 5,14 7,12 21,30 23,28
.0
.0
.0
.0
.0
]dotriacontane-5
[
(
14),6,8,10,12,17,21(30),22,24,26,28-undecaene (D2a). Reaction time
4.1.2.10. (1
a,2b,3a,4b,15b,16a,19b,20a)-6,13,22,29-Tetraaza-
ꢁ
15 min, yield 92%. Mp>300 C; IR (KBr) 3060 (w), 2974 (m), 2942
1,4,15,20-tetrachloro-31,31,32,32-tetramethoxy-9,10,25,26-tetrani-
ꢀ1
14,15 2,19 3,16 5,14 7,12 21,30 23,28
(
(
m), 2924 (m), 2902 (m), 2839 (m), 1511 (m), 1462 (m), 1199 cm
s); H NMR (400 MHz, CDCl
trononcyclo[18.10.1.1.
.0
.0
.0
.0
.0
.0
]do-
1
3
)
d
8.25 (m, 2H), 8.16 (m, 2H), 7.79 (m,
triacontane-5(14),6,8,10,12,17,21(30),22,24,26,28-undecaene
ꢁ
4
H), 5.20 (d, J¼1.0 Hz, 2H), 3.80 (s, 6H), 3.40 (d, J¼10.1 Hz, 2H), 3.39
(D2e). Reaction time 12 h, yield 89%. Mp>300 C; IR (KBr) 3080
13
(
(
(
(
[
(
(
s, 6H), 2.43 (d, J¼10.1 Hz, 2H); C NMR (100 MHz, CDCl
3
)
d
152.3
(m), 3000 (m), 2954 (m), 2898 (w), 2846 (m), 1541 (s), 1353 (s),
ꢀ
1
1
s), 151.6 (s), 142.5 (s), 142.2 (s), 130.0 (d), 129.8 (d), 129.3 (d), 129.3
d),110.5 (s), 75.6 (s), 74.7 (s), 52.3 (q), 52.1 (q), 43.3 (d), 38.1 (d); MS
1197 cm (s); H NMR (400 MHz, CDCl
3
) d 8.84 (s, 2H), 8.73 (s, 2H),
5.25 (d, J¼1.1 Hz, 2H), 3.84 (s, 6H), 3.41 (s, 6H), 3.41 (d, J¼10.1 Hz,
þ
þ
þ
13
FAB) 676 (3) [Mþ6] , 674 (7) [Mþ4] , 672 (6) [Mþ2] , 670 (2)
2H), 2.53 (dd, J¼10.1, 1.1 Hz, 2H); C NMR (100 MHz, CDCl
3
) d 157.5
þ
M] , 154 (100); UV/vis (CHCl
3
)
l
abs
(
e
) 245, 321, 332 nm
(s), 156.8 (s), 143.0 (s), 142.9 (s), 142.7 (s), 142.6 (s), 142.5 (d), 127.3
(d), 124.4 (d), 110.8 (s), 75.5 (s), 74.5 (s), 52.7 (q), 52.5(q), 43.2 (d),
ꢀ
1
3
ꢀ1
70,453 mol dm cm ). Emission (CHCl
3
)
lem 390 nm. HRMS
þ
þ
þ
FAB) calcd for C32
.1.2.7. (1 ,2
H27Cl
4
N
4
O
4
[MþH] : 671.0786; found: 671.0789.
38.1 (d); MS (FAB) 858 (w) [Mþ8] , 856 (w) [Mþ6] , 854 (2)
þ
þ
þ
[
l
Mþ4] , 852 (w) [Mþ2] , 850 (1) [M] , 154 (100); UV/vis (CHCl
3
)
ꢀ
1
3
ꢀ1
4
a
b
,3
a
,4
b
,15
b
,16
a
,19
b
,20
a
)-6,13,22,29-Tetraaza-
abs
(e
) 262 nm (58,220 mol dm cm ). HRMS (FAB) calcd for
23Cl
22Cl
þ
1,4,15,20-tetrachloro-31,31,32,32- tetramethoxy-9,10,25,26-tetrame-
C
C
32
H
4
N
N
8
O
12 [MþH] : 851.0189; found: 851.0198. Anal. Calcd for
14,15
.02,19.03,16.0
5,14 7,12 21,30 23,28
thylnoncyclo[18.10.1.1.
.0
.0
.0
]-do-
32
H
4
8
O
12: C, 45.09; H, 2.60; N, 13.15; O, 22.52; found: C,
triacontane-5(14),6,8,10,12,17,21(30),22,24,26,28-undecaene
45.18; H, 2.79; N, 13.09; O, 22.62.
ꢁ
(
D2b). Reaction time 15 min, yield 94%. Mp>300 C; IR (KBr) 2983
ꢀ1
1
(
w), 2949 (s), 2839 (m), 1499 (s), 1194 cm (s); H NMR (400 MHz,
):
8.01 (s, 2H), 7.91 (s, 2H), 5.17 (d, J¼1.0 Hz, 2H), 3.79 (s, 6H),
.38 (s, 6H), 3.37 (d, J¼10.1 Hz, 2H), 2.51 (s, 6H), 2.48 (s, 6H), 2.41
4.1.2.11. (1
a,2b,3a,4b,19b,20a,23b,24a)-6,17,26,37-Tetraaza-
CDCl
3
(
3
d
1,4,19,24-tetrachloro-39,39,40,40-tetramethoxyundecacyclo
1
4,19 2,23 3,20 5,18 7,16 9,14 25,38 27,36 29,34
[22.14.1.1.
.0
.0
.0
.0
.0
.0
.0
.0
]tetra-
1
3
dd, J¼10.1, 1.1 Hz, 2H); C NMR (100 MHz, CDCl
3
):
d
151.3 (s), 150.7
contane-5(18),6,8,10,12,14,16,21,25(38),26,28,30,32,34,35-pentade-
caene (D2f). Reaction time 15 min, yield 93%. Mp>300 C; IR (KBr)
ꢁ
(
(
2
s), 141.4 (s), 141.0 (s), 140.5 (s), 140.3 (s), 128.7 (d), 128.6 (d), 124.2
d), 110.7 (s), 75.7 (s), 74.9 (s), 52.3 (q), 52.1 (q), 43.5 (d), 38.2 (d),
0.3 (q); MS (FAB) 732 (6) [Mþ6] , 730 (15) [Mþ4] , 728 (14)
3055 (w), 2981 (m), 2947 (m), 2843 (m), 1551 (m), 1456 (m),
þ
þ
ꢀ1
1
3
1189 cm (s); H NMR (400 MHz, CDCl ) d 8.83 (s, 2H), 8.72 (s,
þ
þ
ꢀ
[
3
Mþ2] , 726 (3) [M] , 154 (100); UV/vis (CHCl
3
)
l
abs
(e) 254, 329,
2H), 8.15 (dd, J¼7.8, 2.7 Hz, 2H), 8.10 (dd, J¼7.8, 2.7 Hz, 2H), 7.63
1
3
ꢀ1
44 nm (73,839 mol dm cm ). Emission (CHCl
3
)
lem 380 nm.
(m, 4H), 5.24 (s, 2H), 3.85 (s, 6H), 3.50 (d, J¼10.1 Hz, 2H), 3.43 (s,
þ
13
HRMS (FAB) calcd for C36
H
35Cl
4
N
4
O
4
[MþH] : 727.1412; found:
6H), 2.52 (d, J¼10.1 Hz, 2H); C NMR (100 MHz, CDCl
3
) d 153.0 (s),

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
247
1
52.5 (s), 138.9 (s), 138.5 (s), 133.5 (s), 133.4 (s), 128.3 (d, 2C), 128.0
[22.10.1.14,15.02,23.03,16.05,14.07,12.017,22.025,34.027,32]hexatriacontane-5
(14),6,8,10,12,17(22),18,20,25(34),26,28,30,32-tridecaene
(
d), 127.9 (d), 127.1 (d), 127.1 (d), 124.2 (d), 109.7 (s), 75.6 (s), 74.7
þ
ꢁ
(
7
s), 52.3 (q), 52.1 (q), 43.1 (d), 38.0 (d); MS (FAB) 776 (2) [Mþ6] ,
(D3d). Reaction time 15 min, yield 98%. Mp>300 C; IR (KBr) 3082
þ
þ
þ
ꢀ1
1
74 (5) [Mþ4] , 772 (5) [Mþ2] , 770 (2) [M] , 136 (100); UV/vis
(w), 2982 (m), 2950 (s), 2845 (m), 1474 (s), 1194 cm (s); H NMR
(400 MHz, CDCl 8.32 (s, 2H), 7.82 (s, 2H), 6.94 (m, 2H), 6.89 (m,
2H), 3.86 (s, 6H), 3.76 (d, J¼10.7 Hz, 2H), 3.38 (s, 6H), 3.11 (d,
ꢀ
1
3
ꢀ1
(
CHCl
3
)
l
abs
(
e
) 280, 350, 368 nm (98,362 mol
dm cm ).
3
) d
Emission (CHCl
C
C
3
)
l
em 484 nm. HRMS (FAB) calcd for
þ
13
40
40
H
H
31Cl
30Cl
4
N
4
O
O
4
[MþH] : 771.1099; found: 771.1088. Anal. Calcd for
J¼10.7 Hz, 2H); C NMR (100 MHz, CDCl
3
) d 153.2 (s), 152.9 (s),
4
N
4
4
: C, 62.19; H, 3.91; N, 7.25; O, 8.28; found: C, 62.16;
140.9 (s), 140.7 (s), 134.5 (s), 134.3 (s), 129.8 (d), 129.5 (d), 128.2 (s),
127.6 (d), 127.0 (d), 110.2 (s), 77.5 (s), 75.4 (s), 52.4 (q), 52.4 (q), 46.0
H, 4.14; N, 6.93; O, 8.43.
þ
þ
(
d), 39.1 (d); MS (FAB) 863 (18) [Mþ8] , 861 (24) [Mþ6] , 859 (22)
þ
þ
4
.1.2.12. (1
a
,2
b
,3
a
,4
b
,15
b
,16
a
,23
b
,24
a
)-6,13,26,33-Tetraaza-
[Mþ4] , 857 (10) [Mþ2] , 154 (100); UV/vis (CHCl
3
)
l
abs
(
e) 249,
ꢀ1
3
ꢀ1
1
[
,4,15,24-tetrachloro-35,35,36,36-tetramethoxydecacyclo
344 nm (67,483 mol dm cm ). Emission (CHCl
3
)
lem 391 nm.
22.10.1.14 .0 .0 .0 .0 .0
,15
2,23 3,16 5,14 7,12 17,22 25,34 27,32
.0
.0
]hexatriacontane-5
HRMS (FAB) calcd for C36
856.9382. Anal. Calcd for C36
O, 7.44; found: C, 50.41; H, 3.15; N, 6.41; O, 7.56.
H
25Cl
N
O
[MþH] : 856.9384; found:
þ
8
4
4
(
(
3
14),6,8,10,12,17(22),18,20,25(34),26,28,30,21-tridecaene
D3a). Reaction time 15 min, yield 99%. Mp 287e289 C; IR (KBr)
059 (w), 2974 (m), 2942 (m), 2924 (m), 2902 (m), 2839 (m), 1511
H24Cl
8 4 4
N O : C, 50.26; H, 2.81; N, 6.51;
ꢁ
ꢀ
1
1
(
m), 1462 (m), 1199 cm (s); H NMR (400 MHz, CDCl
J¼8.1 Hz, 2H), 7.71 (m, 4H), 7.61 (dd, J¼8.1 Hz, 2H), 6.87 (dd, J¼6.2,
.4 Hz, 2H), 6.80 (dd, J¼6.2, 3.4 Hz, 2H), 3.87 (s, 6H), 3.81 (d,
3
)
d
8.20 (d,
4.1.2.16. (1
a,2b,3a,4b,15b,16a,23b,24a)-6,13,26,33-Tetraaza-
1,4,15,24-tetrachloro-35,35,36,36-tetramethoxy-9,10,29,30-tetrani-
4
,15 2,23 3,16 5,14 7,12 17,22 25,34 27,32
3
trodecacyclo[22.10.1.1 .0 .0 .0 .0 .0
.0
.0
]hexa-
13
J¼10.7 Hz, 2H), 3.39 (s, 6H), 3.10 (d, J¼10.7 Hz, 2H); C NMR
100 MHz, CDCl 151.8 (s), 151.6 (s), 142.2 (s), 142.1 (s), 129.7 (d),
29.6 (d), 129.1 (d), 128.8 (d), 128.5 (d), 126.8 (d), 110.2 (s), 77.6 (s),
triacontane-5(14),6,8,10,12,17(22),18,20,25(34),26,28,30,32-tride-
ꢁ
(
1
7
3
)
d
caene (D3e). Reaction time 12 h, yield 93%. Mp>300 C; IR (KBr)
ꢀ1
1
3080 (m), 2954 (m), 2846 (m), 1541 (s), 1353 (s), 1197 cm (s); H
NMR (400 MHz, CDCl 8.78 (s, 2H), 8.28 (s, 2H), 7.00 (m, 4H), 3.90
(s, 6H), 3.83 (d, J¼10.7 Hz, 2H), 3.40 (s, 6H), 3.20 (d, J¼10.7 Hz, 2H);
þ
5.5 (s), 52.3 (q), 46.1 (d), 39.2 (d); MS (FAB) 727 (5) [Mþ7] , 725
3
) d
þ
þ
þ
(
(
21) [Mþ5] , 723 (39) [Mþ3] , 721 (29) [Mþ1] , 154 (100); UV/vis
ꢀ
1 3
ꢀ1
13
CHCl
3
)
l
abs
(
l
e
) 245, 320, 331 nm (60,404 mol dm cm ). Emis-
em 390 nm. Anal. Calcd for C36 : C, 59.85; H,
.91; N, 7.76; O, 8.86; found: C, 59.91; H, 3.74; N, 7.60; O, 9.13.
3
C NMR (100 MHz, CDCl ) d 157.1 (s), 156.9 (s), 142.8 (s), 142.5 (s),
sion (CHCl
3
3
)
H
28
C
l4
N
4
O
4
142.4 (s), 142.3 (s), 128.4 (d), 127.6 (s), 127.3 (d), 127.0 (d), 126.6 (d),
110.4 (s), 77.4 (s), 75.3 (s), 52.7 (q), 52.7 (q), 45.7 (d), 39.1 (d); MS
þ
þ
þ
ꢀ
þ
ꢀ1
(
FAB) 906 (1) [Mþ6] , 904 (1) [Mþ4] , 902 (2) [Mþ2] , 900 (1) [M] ,
1 3
4
.1.2.13. (1
a
,2
b
,3
a
,4
b
,15
b
,16
a
,23
b
,24
a
)-6,13,26,33-Tetraaza-
154 (100); UV/vis (CHCl
3
)
l
abs
(e
) 261 nm (34,834 mol dm cm ).
þ
1,4,15,24-tetrachloro-35,35,36,36-tetramethoxy-9,10,29,30-tetrame-
HRMS (FAB) calcd for C36
901.0342. Anal. Calcd for C36
N, 12.42; O, 21.27; found: C, 47.96; H, 2.68; N, 12.46; O, 21.16.
H25Cl
4
N
8
O
12 [MþH] : 901.0346; found:
4
,15 2,23 3,16 5,14 7,12 17,22 25,34 27,32
thyldecacyclo[22.10.1.1 .0 .0 .0 .0 .0
tricontane-5(14),6,8,10,12,17(22),18,20,25(34),26,28,30,32-tridecaene
.0
.0
]hexa-
H24Cl
4 8
N O12 (902.43): C, 47.91; H, 2.68;
ꢁ
(D3b). Reaction time 15 min, yield 95%. Mp>300 C; IR (KBr) 2949
ꢀ1
1
(
s), 2839 (m), 1499 (s), 1194 cm (s); H NMR (400 MHz, CDCl
3
)
4.1.2.17. (1
a,2b,3a,4b,19b,20a,27b,28a)-6,17,30,41-Tetraaza-
d
7.94 (s, 2H), 7.45 (s, 2H), 6.89 (dd, J¼6.2, 3.4 Hz, 2H), 6.85 (dd, J¼6.2,
1,4,19,28-tetrachloro-43,43,44,44-tetramethoxydodecacyclo
14,19 2,27 3,20 5,18 7,16 9,14 21,26 29,42 31,40 33,38
3
.4 Hz, 2H), 3.85 (s, 6H), 3.77 (d, J¼10.7 Hz, 2H), 3.37 (s, 6H), 3.09 (d,
[26.14.1.
.0 .0 .0 .0 .0 .0
.0
.0
.0
]tetrate-
13
J¼10.7 Hz, 2H), 2.46 (s, 6H), 2.36 (s, 6H); C NMR (100 MHz, CDCl
150.8 (s), 150.5 (s), 141.1 (s), 140.9 (s), 140.1 (s), 139.9 (s), 128.7 (d),
28.3 (d),128.1 (s),127.1 (d),126.9 (d),110.3 (s), 77.8 (s), 75.6 (s), 52.3
q), 52.3 (q), 46.1 (d), 39.2 (d), 20.3 (q), 20.2 (q); MS (FAB) 784 (7)
3
)
t r a c o n t a n e - 5 ( 18 ) , 6 , 8 , 10 , 1 2 , 14 , 16 , 2 1 ( 2 6 ) , 2 2 , 2 4 , 2 9
d
(42),30,32,34,36,38,40-heptadecaene (D3f). Reaction time 15 min,
ꢁ
1
(
yield 95%. Mp>300 C; IR (KBr) 3055 (w), 2981 (m), 2947 (m), 2843
ꢀ1
1
3
(m), 1551 (m), 1456 (m), 1189 cm (s); H NMR (400 MHz, CDCl )
þ
þ
þ
[
l
l
Mþ8] , 780 (24) [Mþ4] , 776 (9) [M] , 154 (100); UV/vis (CHCl
3
)
)
d
8.78 (s, 2H), 8.26 (s, 2H), 8.11 (d, J¼8.1 Hz, 2H), 7.96 (d, J¼8.1 Hz,
ꢀ
1
3
ꢀ1
abs
(e
) 254, 329, 344 nm (61,442 mol dm cm ). Emission (CHCl
em 380 nm. HRMS (FAB) calcd for C40
3
2H), 7.57 (m, 4H), 6.86 (dd, J¼6.2, 3.4 Hz, 2H), 6.79 (dd, J¼6.2, 3.4 Hz,
2H), 3.91 (s, 6H), 3.90 (d, J¼10.7 Hz, 2H), 3.43 (s, 6H), 3.22 (d,
þ
H
H
37Cl
36Cl
4
N
4
O
O
4
[MþH] :777.1563;
13
found: 777.1566. Anal. Calcd for C40
4
4
N
4
4
(778.55): C, 61.71; H,
J¼10.7 Hz, 2H); C NMR (100 MHz, CDCl
3
) d 152.4 (s), 152.2 (s),
.66; N, 7.20; O, 8.22; found: C, 61.60; H, 4.65; N, 6.97; O, 8.17.
138.3 (s), 138.3 (s) 133.1 (s), 133.0 (s), 128.2 (d), 128.1 (d), 128.1 (d),
27.4 (d), 127.2 (d), 127.1 (d), 126.7 (d), 126.7 (d), 126.6 (d), 109.1 (s),
77.4 (s), 75.3 (s), 52.1 (q), 52.1 (q), 45.7 (d), 38.8 (d); MS (FAB): 828
1
4
.1.2.14. (1
a,2b,3a,4b,15b,16a,23b,24a)-6,13,26,33-Tetraaza-
þ
þ
þ
þ
1
,4,15,24-tetrachloro-9,10,29,30,35, 35,36,36-octamethoxydecacyclo
(2) [Mþ8] , 826 (8) [Mþ6] , 824 (16) [Mþ4] , 822 (16) [Mþ2] ,
22.10.1.14 .0 .0 .0 .0 .017,22.0
,15
2,23 3,16 5,14 7,12
25,34 27,32
.0
]hexatriacontane-5
820 (5) [M] , 136 (100); UV/vis (CHCl
þ
)
l
(
)
e
) 280, 351, 368 nm
em 484 nm. HRMS
[
(
(
(
3
abs
ꢀ
1
3
ꢀ1
14),6,8,10,12,17(22),18,20,25(34),26,28,30,32-tridecaene
D3c). Reaction time 15 min, yield 91%. Mp>300 C; IR (KBr) 2948
s), 2844 (m),1631 (m),1504 (s),1469 (s),1429 (s),1243 cm (s); H
7.50 (s, 2H), 7.00 (s, 2H), 6.88 (m, 4H), 4.06
(153,621 mol dm cm ). Emission (CHCl
(FAB) calcd for C44
Anal. Calcd for C44
3
l
ꢁ
þ
H33Cl
4
N
4
O
4
[MþH] : 821.1256; found: 821.1258.
ꢀ
1
1
H32Cl
4
N
4
O
4
: C, 64.25; H, 3.92; N, 6.81; O, 7.78;
NMR (400 MHz, CDCl
3
)
d
found: C, 64.64; H, 3.91; N, 6.77; O, 7.92.
(
3
s, 6H), 3.88 (s, 6H), 3.85 (s, 6H), 3.76 (d, J¼10.7 Hz, 2H), 3.38 (s, 6H),
13
.09 (d, J¼10.7 Hz, 2H); C NMR (100 MHz, CDCl
3
)
d
152.2 (s), 152.1
4.1.2.18. (1
a,2b,3a,4b,15b,16a,19b,20a)-6,8,13,22,27,29-Hexaaza-
(
(
s), 149.3 (s), 148.9 (s), 139.2 (s), 139.0 (s), 128.9 (s), 127.0 (d), 126.9
d), 110.7 (s), 107.2 (d), 107.0 (d), 77.8 (s), 75.7 (s), 56.4 (q), 56.3 (q),
1,4,15,20-tetrachloro-31,31,32,32-tetramethoxynoncyclo
4
,15 2,19 3,16 5,14 7,12 21,30 23,28
[18.10.1.1
.0
.0
.0
.0
.0
.0
]dotriacontane-5
(D2g ). Reaction
þ
5
2.3 (q), 52.2 (q), 46.5 (d), 39.3 (d); MS (FAB) 848 (w) [Mþ8] , 842
(14),6,8,10,12,17,21(30),22,24,26,28-undecaene
time 8 h, yield 81%. Mp 280e281 C; IR (KBr): 2952 (m), 2848 (w),
1738 (s), 1500 (s), 1195 (s); H NMR (400 MHz, CDCl ): d 9.18 (dd,
3
a
þ
þ
ꢁ
(
3
1) [Mþ2] , 840 (1) [M] , 154 (100); UV/vis (CHCl
3
)
)
l
abs
(
e
) 250,
ꢀ1
3
ꢀ1
1
61 nm (37,357 mol dm cm ). Emission (CHCl
3
lem 381 nm.
þ
HRMS (FAB) calcd for C40
8
H
37Cl
4
N
4
O
8
[MþH] : 841.1391; found:
J¼4.2, 1.9 Hz, 2H), 8.52 (dd, J¼8.3, 1.9 Hz, 2H), 7.76 (dd, J¼8.3, 4.2 Hz,
41.1378. Anal. Calcd for C40
H
36Cl
4
N
4
O
8
: C, 57.02; H, 4.31; N, 6.65;
2H), 5.17 (d, J¼1.1 Hz, 2H), 3.80 (s, 6H), 3.53 (d, J¼10.1 Hz, 2H),3.37 (s,
13
O, 15.19; found: C, 56.69; H, 4.13; N, 6.62; O, 15.27.
6H), 2.50 (dd, J¼10.1,1.1 Hz, 2H); C NMR (100 MHz, CDCl
3
): d 155.4
(s),154.1 (s),153.0 (d),151.5 (s),138.4 (s),137.7 (d),125.3(d),124.5(d),
4
.1.2.15. (1
a,2b,3a,4b,15b,16a,23b,24a)-6,13,26,33-Tetraaza-
110.8 (s), 75.5 (s), 74.8 (s), 52.4 (q), 52.3 (q), 43.4(d), 38.1 (d); UV/vis
ꢀ ꢀ1
1
3
1
,4,9,10,15,24,29,30-octachloro-35, 35,36,36-tetramethoxydecacyclo
(mixture, CDCl ): l (e) 310, 323 nm (46,318 mol dm cm ); MS
3 abs

248
T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
þ
þ
þ
(
FAB): 678 (25) [Mþ6] , 676 (62) [Mþ4] , 672 (7) [M] , 154 (100);
J¼8.3, 4.2 Hz, 2H), 6.86 (dd, J¼6.2, 3.4 Hz, 2H), 6.84 (dd, J¼6.2,
3.4 Hz, 2H), 3.93 (d, J¼10.7 Hz, 2H), 3.87 (s, 6H), 3.39 (s, 6H), 3.23 (d,
þ
HMRS (FAB) calcd for C30
73.0696. Anal. Calcd for C30
N, 12.46; O, 9.49; found: C, 53.25; H, 3.86; N, 12.26; O, 9.21.
H25Cl
4
N
6
O
4
[MþH] : 673.0701, found:
13
6
H24Cl
4
N
6
O
4
(672.39): C, 53.43; H, 3.59;
J¼10.7 Hz, 2H); C NMR (100 MHz, CDCl
3
): d 155.4 (s), 153.7 (s),
152.7 (d), 150.9 (s), 138.1 (s), 137.6 (d), 128.7 (s), 127.4 (d), 126.9 (d),
25.1 (d), 110.4 (s), 77.6 (s), 75.3 (s), 52.5 (q), 52.4 (q), 45.8 (d), 39.1
1
4
.1.2.19. (1
a
,2
b
,3
a
,4
b
,15
b
,16
a
,23
b
,24
a
)-6,8,13,26,31,33-Hexaaza-
(d); UV/vis (mixture, CHCl
3
):
l
abs
(
e
)
311, 325 nm
ꢀ
1
3
ꢀ1
þ
1
,4,15,24-tetrachloro-35,35,36, 36-tetramethoxydecacyclo[22.10.1.1
(47,406 mol dm cm ); MS (FAB) 730 (17) [Mþ8] , 728 (32)
4
,15 2,23 3,16 5,14 7,12
.017,22.0
25,34 27,32
þ
þ
þ
þ
.
0
.0
.0
.0
.0
]hexatria-contane-5
[Mþ6] , 726 (73) [Mþ4] , 725 (100) [MþHþ2] , 724 (47) [Mþ2] ,
þ
þ
(
14),6,8,10,12,17(22),18,20,25(34),26,28,30,21-tridecaene (D3g
Reaction time 8 h, yield 76%. Mp 280e281 C; IR (KBr): 2952 (m),
848 (w), 1738 (s), 1500 (s), 1195 (s); H NMR (400 MHz, CDCl
9.10 (dd, J¼4.2, 1.9 Hz, 2H), 8.08 (dd, J¼8.3, 1.9 Hz, 2H), 7.60 (dd,
a). -
722 (11) [M] ; HMRS (FAB) calcd for C34
H
27Cl
4
N
6
O
4
[MþH] :
ꢁ
723.0848, found: 723.0852. Anal. Calcd for C34
C, 56.37; H, 3.62; N, 11.60; O, 8.83; found: C, 56.38; H, 3.85; N, 11.84;
O, 8.64.
H
26Cl
4
N
6
O
4
(724.42):
1
2
d
3
):
Table 3
Crystal data and structure refinement for compounds D1a, D2a, D2f, D3f, D2g-
a
, and D3g-
a
Identification code
Empirical formula
Formula weight
Crystal size [mm]
Temperature [K]
D1a
D2a
D2f
C
34
H
32Cl
N
4 4
O
4
eCH
2
Cl
2
C
32
H
32Cl
4
4
N O
4
C
40
H
30Cl
N
4 4
O
4
ꢀ2CHCl
3
787.36
0.1ꢂ0.1ꢂ0.1
273(2)
672.37
0.1ꢂ0.2ꢂ0.2
273(2)
1011.22
0.1ꢂ0.2ꢂ0.2
273(2)
ꢀ
Wavelength [A]
0.71073
0.71073
0.71073
Crystal system, Space group
Unit cell dimensions
Monoclinic, P2(1)/c
Orthorhombic, Pca2(1)
Monoclinic, C2/c
ꢀ
ꢀ
ꢀ
a¼11.8176(5) A
a¼19.142(8) A
a¼23.6348(19) A
ꢀ
ꢀ
ꢀ
b¼12.8470(6) A
b¼8.024(3) A
b¼8.1528(6) A
ꢀ
ꢀ
ꢀ
c¼23.9534(11) A
c¼19.142(8) A
c¼23.8433(19) A
ꢁ
ꢁ
ꢁ
ꢁ
a
¼90
a
¼90
a
¼90
ꢁ
ꢁ
b
¼102.6280(10)
b¼90
b
¼107.666(2)
ꢁ
ꢁ
ꢁ
g
¼90
g
¼90
g
¼90
ꢀ
3
Volume [A ]
3548.7(3)
4
2940(2)
4377.7(6)
4
Z
4
3
Density (calcd) [mg/m ]
1.474
0.530
1.519
0.450
1.534
0.685
Absorption coefficient [mmꢀ1]
F(000)
1624
1.74e28.29
1384
2.13e28.38
2056
1.79e28.33
ꢁ
q
range for data collection [ ]
Index ranges
Reflections collected
Independent reflections
ꢀ15ꢃhꢃ15, ꢀ16ꢃkꢃ16, ꢀ31ꢃlꢃ31
ꢀ24ꢃhꢃ25,ꢀ10ꢃkꢃ10, ꢀ25ꢃlꢃ25
ꢀ31ꢃhꢃ30,ꢀ10ꢃkꢃ10, ꢀ31ꢃlꢃ31
31,111
24,551
24,551
8579[Rint¼0.0276]
97.2%
Full-matrix least-squares on F2
8579/0/447
6986[Rint¼0.1018]
97.2%
Full-matrix least-squares on F2
6986/1/401
5315[Rint¼0.0543]
97.4%
Full-matrix least-squares on F2
6986/1/401
Completeness to
q
¼28.29
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I>2(I)]
R indices (all data)
1.076
1.054
1.652
R1¼0.0380, wR2¼0.1124
R1¼0.0440, wR2¼0.1155
0.386, ꢀ0.340
R1¼0.0448, wR2¼0.1050
R1¼0.0481, wR2¼0.1064
0.375 and ꢀ0.498
R1¼0.1397, wR2¼0.4183
R1¼0.1651, wR2¼0.4384
2.911 and ꢀ1.301
ꢀ
ꢀ3
O
r
max,
O
rmin [e A
]
Identification code
Empirical formula
Formula weight
Crystal size [mm]
Temperature [K]
D3f
D2g-
a
D3g-
a
C
44
H
32Cl
4
4
N O
4
ꢀ2CHCl
3
C
30
H
24Cl
N
4 6
O
4
C
34
4 6 4 3
H26Cl N O eCHCl
1061.27
0.1ꢂ0.2ꢂ0.2
273(2)
674.35
843.78
0.1ꢂ0.2ꢂ0.2
0.1ꢂ0.2ꢂ0.2
273(2)
273(2)
ꢀ
Wavelength [A]
0.71073
0.71073
0.71073
Crystal system, Space group
Unit cell dimensions
Triclinic, Pꢀ1
Monoclinic, P2(1)/n
Monoclinic, P2(1)/c
ꢀ
ꢀ
ꢀ
a¼12.0776(5) A
a¼13.5230(10) A
a¼20.4398(11) A
ꢀ
ꢀ
ꢀ
b¼14.6795(7) A
b¼15.6055(12) A
b¼10.9182(6) A
ꢀ
ꢀ
ꢀ
c¼15.1588(7) A
c¼15.0180(12) A
c¼17.6546(9) A
ꢁ
ꢁ
ꢁ
ꢁ
ꢁ
a
¼71.2790(10)
a
¼90
a
¼90
ꢁ
ꢁ
b
¼78.3720(10)
b
¼113.2470(10)
b
¼112.2060(10)
ꢁ
ꢁ
g
¼67.2760(10)
g
¼90
g
¼90
ꢀ
3
Volume [A ]
2338.51(18)
2
2912.0(4)
4
3647.7(3)
4
Z
3
Density (calcd) [mg/m ]
1.507
0.645
1.538
0.456
1.536
0.594
Absorption coefficient [mmꢀ1]
F(000)
1080
1.56e28.28
1384
1.72e28.30
1720
1.08e28.34
ꢁ
q
range for data collection [ ]
Index ranges
Reflections collected
Independent reflections
ꢀ16ꢃhꢃ15,ꢀ19ꢃkꢃ18, ꢀ19ꢃlꢃ20
ꢀ16ꢃhꢃ17,ꢀ20ꢃkꢃ20, ꢀ19ꢃlꢃ19
ꢀ27ꢃhꢃ27,ꢀ14ꢃkꢃ14, ꢀ23ꢃlꢃ23
20,973
25,592
31,713
10,833 [Rint¼0.0286]
7057[Rint¼0.0456]
97.6%
8795[Rint¼0.0633]
96.5%
Completeness to
q
¼28.29
93.4%
2
Full-matrix least-squares on F2
7057/0/402
Full-matrix least-squares on F2
8795/0/474
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I>2(I)]
R indices (all data)
Full-matrix least-squares on F
10,833/0/582
1.194
R1¼0.1001, wR2¼0.2678
R1¼0.1050, wR2¼0.2720
0.933 and ꢀ1.274
1.078
1.023
R1¼0.0405, wR2¼0.1212
R1¼0.0446, wR2¼0.1245
0.939 and ꢀ0.325
R1¼0.0746, wR2¼0.2179
R1¼0.1274, wR2¼0.2455
0.930 and ꢀ0.600
ꢀ
ꢀ3
O
r
max,
O
rmin [e A ]
R¼S||F
o
|ꢀ|F
c
||/S|F |.
o
2
2
2
2
wR2¼[Sw(F
o
ꢀF

T.-C. Chou, K.-C. Liao / Tetrahedron 67 (2011) 236e249
249
4
.2. X-ray crystallography
Chem. 2000, 13, 604e611; (e) Rowan, A. E.; Elemans, J. A. A. W.; Nolte, R. J. M.
Acc. Chem. Res. 1999, 32, 995e1006; (f) Mataka, S.; Shigaki, K.; Sawada, T.;
Mitoma, Y.; Taniguchi, M.; Thiemann, T.; Ohga, K.; Egashira, N. Angew. Chem.,
Int. Ed. 1998, 37, 2532e2534; (g) Mataka, S.; Mitoma, Y.; Thiemann, T.; Sawada,
T.; Taniguchi, M.; Kobuchi, M.; Tashiro, M. Tetrahedron 1997, 53, 3015e3026.
7. (a) Head, N. J.; Oliver, A. M.; Look, K.; Lokan, N. R.; Jones, G. A.; Paddon-Row, M.
N. Angew. Chem., Int. Ed. 1999, 38, 3219e3222; (b) Paddon-Row, M. N. Acc. Chem.
Res. 1994, 27, 18e25.
The X-ray crystallographic data were recorded with a Bruker AXS
SMART APEX CCD X-ray diffractometer. Graphite monochromatized
Mo K
used. The CCD data were processed with SAINT and the structures
were solved by direct method (SHELXS-97) and refined on F by full-
matrix least-squarestechniques (SHELXL-97). Crystaldata/structure
refinement are compiled in Table 3.
ꢀ
a
radiation [l¼0.71073 A] and temperature of 298 (2) K were
2
8. (a) She, N.; Gao, M.; Cao, L.; Wu, A.; Isaacs, L. Org. Lett. 2009, 11, 2603e2606; (b)
Stancl, M.; Necas, M.; Taraba, J.; Sindelar, V. J. Org. Chem. 2008, 73, 4671e4675;
(
c) Branchi, B.; Balzani, V.; Ceroni, P.; Kuchenbrandt, M. C.; Kl a€ rner, F.-G.; Bl a€ ser,
D.; Boese, R. J. Org. Chem. 2008, 73, 5839e5851; (d) Reek, J. N. H.; Elemans, J. A.
A. W.; de Gelder, R.; Beurskens, P. T.; Rowan, A. E.; Nolte, R. J. M. Tetrahedron
2
003, 59, 175e185.
Acknowledgements
9
. (a) Kl €a rner, F.-G.; Kahlert, B.; Boese, R.; Bl a€ ser, D.; Juris, A.; Marchioni, F. Chem.
Eur. J. 2005, 11, 3363e3374; (b) Kl €a rner, F.-G.; Burkert, U.; Kamieth, M.; Boese,
R.; Benet-Buchholz, J. Chem.dEur. J. 1999, 5, 1700e1707; (c) Kurebayashi, H.;
Sakaguchi, M.; Okajima, T.; Haino, T.; Usui, S.; Fukazawa, Y. Tetrahedron Lett.
The financial support from the National Science Council of Tai-
wan is gratefully acknowledged.
1
999, 40, 5545e5548.
0. (a) Chou, T.-C.; Liao, K.-C.; Lin, J.-J. Org. Lett. 2005, 7, 4843e4846; (b) Chou, T.-C.;
Lin, K.-C.; Wu, C.-A. Tetrahedron 2009, 65, 10243e10257.
1
Supplementary data
1
1. (a) Khan, F. A.; Prabhudas, B.; Dash, J. J. Prakt. Chem. 2000, 342, 512e517; (b)
Ungnade, H. E.; McBee, E. T. Chem. Rev. 1958, 58, 249e320.
The experimental section (general) and proton NMR spectra of
the Z-shaped quadruple-bridged [6,6] and [6,4]orthocyclophanes.
Supplementary data associated with this article can be found in the
online version, at doi:10.1016/j.tet.2010.10.065.
1
2. (a) Khan, F. A.; Dash, J.; Sudheer, C.; Sahu, N.; Parasuraman, K. J. Org. Chem.
005, 70, 7565e7577; (b) Khan, F. A.; Dash, J. J. Am. Chem. Soc. 2002, 124,
2424e2425; (c) Khan, F. A.; Prabhudas, B.; Dash, J.; Sahu, N. J. Am. Chem. Soc.
000, 122, 9558e9559.
3. (a) Garcia, J. G.; Fronczek, F. R.; McLaughlin, M. L. Tetrahedron Lett. 1991, 32,
289e3292.
14. (a) Shibata, K.; Kulkarni, A. A.; Ho, D. M.; Pascal, R. A., Jr. J. Am. Chem. Soc. 1994,
16, 5983e5984; (b) Danish, A. A.; Silverman, M.; Tajima, Y. A. J. Am. Chem. Soc.
954, 76, 6144e6150.
5. Chou, T.-C.; Hong, P.-C.; Lin, C.-T. Tetrahedron Lett. 1991, 32, 6351e6354.
6. Chou, T.-C.; Chiou, J.-H. J. Chin. Chem. Soc. 1986, 33, 227e234.
7. (a) Mataka, S.; Mimura, T.; Lee, S. T.; Kobayashi, H.; Takahashi, K.; Tashiro, M. J.
2
2
1
3
References and notes
1
1
1. (a) Meyer, E. A.; Castellano, R. K.; Diederich, F. Angew. Chem., Int. Ed. 2003, 42,
1
1
1
1210e1250; (b) Desiraju, G. R. Acc. Chem. Res. 2002, 35, 565e573; (c) Desiraju,
G. R. Acc. Chem. Res. 1996, 29, 441e449; (d) Taylor, B.; Kennard, O. Acc. Chem.
Res. 1984, 17, 320e326.
Org. Chem. 1989, 54, 5237e5241; (b) Mataka, S.; Takahashi, K.; Mimura, T.;
Hirota, T.; Takuma, K.; Kobayashi, H.; Tashiro, M.; Imada, K.; Kuniyoshi, M. J. Org.
Chem. 1987, 52, 2653e2656.
2. (a) Jennings, W. B.; Farrell, B. M.; Malone, J. F. Acc. Chem. Res. 2001, 34, 885e894;
(
b) Dunitz, J. D.; Gavezzotti, A. Acc. Chem. Res. 1999, 32, 677e684; (c) Ma, J. C.;
Dougherty, D. A. Chem. Rev. 1997, 97, 1303e1324; (d) Jorgensen, W. L.; Sever-
ance, D. L. J. Am. Chem. Soc. 1990, 112, 4768e4774; (e) Hunter, C. A.; Sanders, J.
K. M. J. Am. Chem. Soc. 1990, 112, 5525e5534; (f) Nishio, M.; Umezawa, Y.;
Hirota, M.; Takeuchi, Y. Tetrahedron 1995, 51, 8665e8701; (g) Nishio, M.; Hirota,
M. Tetrahedron 1989, 45, 7201e7245; (h) Cram, D. J.; Cram, J. M. Acc. Chem. Res.
1
8. Crystallographic data (excluding structure factors) for D1a, D2a, D2f, D3f,
D2g- , and D3g- have been deposited with the Cambridge Crystallographic
Data Centre as supplementary publication numbers CCDC 787937, CCDC
87936, CCDC 787935, CCDC 787933, CCDC 787934, and CCDC787932,
respectively.
a
a
7
1971, 4, 204e213.
1
9. (a) Dorofeeva, O. V.; Mastryukov, V. S.; Allinger, N. L.; Almenningen, A. J. Phys.
Chem. 1985, 89, 252e257; (b) Hendrickson, J. B. J. Am. Chem. Soc. 1967, 89,
3
. (a) Boussicault, F.; Robert, M. Chem. Rev. 2008, 108, 2622e2645; (b) Burley, S. K.;
Petsko, G. A. Adv. Protein Chem. 1988, 39, 125e189; (c) Burley, S. K.; Petsko, G. A.
Science 1985, 229, 23e28; (d) Fokkens, M.; Jasper, C.; Schrader, T.; Koziol, F.;
Ochsenfeld, C.; Polkowska, J.; Lobert, M.; Kahlert, B.; Kl €a rner, F.-G. Chem.dEur. J.
7
036e7043.
0. Chiang, J. F.; Bauer, S. H. J. Am. Chem. Soc. 1969, 91, 1898e1901.
1. Hydrogen bond is referred to the noncovalent interactions having interatomic
2
2
2
1
8
005,11, 477e494; (e) Kim, E.-i.; Paliwal, S.;Wilcox, C. S. J. Am. Chem. Soc.1998,120,
1192e11193; (f) Adrian, J. C., Jr.; Wilcox, C. S. J. Am. Chem. Soc. 1989, 111,
055e8059.
ꢀ
ꢀ
distance shorter than the sum of the van der Waals radii of hydrogen (1.20 A)
ꢀ
ꢀ
ꢀ
and carbon (1.70 A), nitrogen (1.55 A), oxygen (1.52 A), or chlorine (1.75 A)
atoms.22 Arbitrarily, we refer others having interatomic distance longer by
about 25% as close contacts.
4
5
. (a) Harmata, M. Acc. Chem. Res. 2004, 37, 862e873; (b) Kl €a ner, F.-G.; Kahlert, B.
Acc. Chem. Res. 2003, 36, 919e932; (c) Fyfe, M. C. T.; Stoddart, J. F. Acc. Chem. Res.
2
2. (a) Pauling, L. The Nature of the Chemical Bonds; Cornel University: Ithaca, New
York, NY, 1960; p 260; (b) Bondi, A. J. Phys. Chem. 1964, 68, 441e451.
3. (a) Paliwal, S.; Geib, S.; Wilcox, C. S. J. Am. Chem. Soc. 1994, 116, 4497e4498; (b)
Kobayashi, K.; Asakawa, Y.; Kikuchi, Y.; Toi, H.; Aoyama, Y. J. Am. Chem. Soc.
1997, 30, 393e401; (d) Hunter, C. A. Chem. Soc. Rev. 1994, 101e109; (e) Cram, D.
J.; Bauer, R. H. J. Am. Chem. Soc. 1959, 81, 5971e5977.
. (a) Chen, Y.; She, N.; Meng, X.; Yin, G.; Wu, A.; Isaacs, L. Org. Lett. 2007, 9,
2
1899e1902; (b) Kawase, T.; Kurata, H. Chem. Rev. 2006, 106, 5250e5273; (c)
1993, 115, 2648e2654; (c) Adams, H.; Carver, F. J.; Hunter, C. A.; Morales, J. C.;
Wang, Z.-G.; Zhou, B.-H.; Chen, Y.-F.; Yin, G.-D.; Li, Y.-T.; Wu, A.-X.; Isaacs, L. J.
Org. Chem. 2006, 71, 4502e4508; (d) Rebek, J., Jr. Acc. Chem. Res. 1999, 32,
Seward, E. M. Angew. Chem., Int. Ed. Engl. 1996, 35, 1542e1544.
4. Taylor, B.; Kennard, O. J. Am. Chem. Soc. 1982, 104, 5063e5070.
5. (a) Gung, B. W.; Xue, X.; Reich, H. J. J. Org. Chem. 2005, 70, 3641e3644; (b)
Sindkhedkar, M. D.; Mulla, H. R.; Cammers-Goodwin, A. J. Am. Chem. Soc. 2000,
2
2
278e286.
6
. (a) Shibahara, M.; Watanabe, M.; Suenaga, M.; Ideta, K.; Matsumoto, T.; Shin-
myozu, T. Tetrahedron Lett. 2009, 50, 1340e1344; (b) Muranaka, A.; Shibahara,
M.; Watanabe, M.; Matsumoto, T.; Shinmyozu, T.; Kobayashi, N. J. Org. Chem.
122, 9271e9277.
2
6. (a) Carroll, W. R.; Pellechia, P.; Shimizu, K. D. Org. Lett. 2008, 10, 3547e3550; (b)
Alkorta, I.; Blanco, F.; Elguero, J. Tetrahedron Lett. 2008, 49, 7246e7249.
2
3
008, 73, 9125e9128; (c) Wong, W. W. H.; Diederich, F. Chem.dEur. J. 2006, 12,
463e3471; (d) Kl €a rner, F.-G.; Burket, U.; Kamieth, M.; Boese, R. J. Phys. Org.