Synthesis of multivalent oxamate ligands based on calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation

Article abstract of DOI:10.1016/j.tet.2017.05.043

Five new multivalent ligands based on either p-tert-butylthiacalix[4]arene (TCA) 1 or p-tert-butylcalix[4]arene (CA) 2 backbones in 1,3-Alternate conformation bearing four oxamate coordinating groups at their lower rim were designed and synthesized by a multistep strategy. These ligands differ either by the nature of the calix[4]arene backbone (CA or TCA) or by the nature of the spacer ((CH₂)_n) connecting the oxamate binding units to the backbone.

Full text of DOI:10.1016/j.tet.2017.05.043

Accepted Manuscript
Synthesis of multivalent oxamate ligands based on calix[4]arene and thiacalix[4]arene
backbones in 1,3-Alternate conformation
Mohamed Habib Noamane, Sylvie Ferlay, Rym Abidi, Mir Wais Hosseini
PII:
S0040-4020(17)30519-7
10.1016/j.tet.2017.05.043
TET 28709
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 20 April 2017
Revised Date: 9 May 2017
Accepted Date: 10 May 2017
Please cite this article as: Noamane MH, Ferlay S, Abidi R, Hosseini MW, Synthesis of multivalent
oxamate ligands based on calix[4]arene and thiacalix[4]arene backbones in 1,3-Alternate conformation,
Tetrahedron (2017), doi: 10.1016/j.tet.2017.05.043.
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Synthesis of multivalent oxamate ligands
based on calix[4]arene and thiacalix[4]arene
backbones in 1,3-Alternate conformation
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*
*
Mohamed Habib Noamane, Sylvie Ferlay , Rym Abidi, Mir Wais Hosseini

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Tetrahedron
journal homepage: www.elsevier.com
Synthesis of multivalent oxamate ligands based on calix[4]arene and thiacalix[4]arene
backbones in 1,3-Alternate conformation
a,b
a,*
b
a,*
Mohamed Habib Noamane , Sylvie Ferlay , Rym Abidi , Mir Wais Hosseini
a
Molecular Tectonics Laboratory, Université de Strasbourg, CNRS, CMC UMR 7140, F-67000 Strasbourg, France
Université de Carthage, Laboratoire d'Application de la Chimie aux Ressources
et Substances Naturelles et à l'Environnement (LACReSNE), unité des
b
interactions moléculaires spécifiques, Faculté des Sciences de Bizerte, 7021 Bizerte, Tunisia
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
Five new multivalent ligands based on either p-tert-butylthiacalix[4]arene (TCA) 1 or p-tert-
butylcalix[4]arene (CA) 2 backbones in 1,3-Alternate conformation bearing four oxamate
coordinating groups at their lower rim were designed and synthesized by a multistep strategy.
These ligands differ either by the nature of the calix[4]arene backbone (CA or TCA) or by the
Available online
nature of the spacer ((CH
2
)
n
) connecting the oxamate binding units to the backbone.
2
009 Elsevier Ltd. All rights reserved
.
Keywords:
Calix[4]arenes
Thiacalix[4]arenes
Oxamate ligand
1
,3-Alternate conformation
Phthalimide
1
. Introduction
For the design of multivalent ligands, calixarenes,
thiacalix[4]arene backbone, the thioether junctions may be
5
6
oxidized to sulfonyl (X = SO) or sulfinyl (X = SO ). Among the
1
2
four limit conformations adopted by CA and TCA, the 1,3-
Alternate conformation is of interest for the design of multivalent
entities since it allows to position four interactions below and
above the macrocyclic backbone in an alternate fashion. We shall
focus here on calix based coordinating derivatives. Both
calix[4]arene and thiacalix[4]arene have been decorated both at
the upper and/or lower rims with a variety of monodentate donor
macrocyclic organic entities based on interconnection of phenolic
moieties by CH groups, are of particular interest. Indeed, this
class of preorganized backbone offers unlimited design
possibilities through functionalization of the lower and/or upper
rims. Furthermore, the CH moiety connecting the phenolic units
may be replaced by other groups or atoms. Calixarene derivatives2
have been widely used in the field of supramolecular chemistry
for substrate binding, recognition and transport of neutral
2
2
7
8
9
sites (cyano, pyridine, pyrazole, etc..) as well as bidendate
(
10
11
12
bipyridine, carboxylate, , ethylene diamine, etc..) units.
3
molecules or ions.
These polydentate ligands have been used for the formation of
13
discrete coordination complexes
or infinite coordination
Among the calix[n]arene derivatives, differing by the number
polymers. Among bis-bidentate N and/or O donor units such as
bis-pyrimidine, chloranilate, oxalate and oxamate ligand, the
latter has been widely used for the synthesis of a variety of
of phenolic units (n = 4-12), thiacalix[4]arene (TCA, 1, Figure
1
4
), for which the four aryl rings are connected by thioether
1
junctions and calix[4]arene (CA, 2, Figure 1) are of interest
owing to their conformational flexibility leading to four limit
conformers called cone, partial cone, 1,2-Alternate and 1,3-
Alternate. This aspect may be exploited for the design of
multivalent ligands for which the interaction sites are positioned
either on the same face of the backbone (cone conformer) or
distributed on both sides of the mean plane of the macrocyclic
framework (partial cone, 1,2-Alternate and 1,3-Alternate
conformers). As stated above, both compounds 1 and 2 may be
readily modified allowing thus the design of a large variety of
receptors and ligands. Indeed, both backbones may be equipped
with interaction sites at both at the lower rim though
functionalization of the OH groups or at upper rim by
introduction of almost any group at the para position. For the
14
coordination complexes used in 16catalysis,
molecular
15
magnetism and in medicinal chemistry.
To the best of our knowledge, no example of calix[4]arene
bearing oxamate coordinating groups has been reported to date.
Furthermore, no examples of ligands based on tetrasubstituted
CA or TCA 1,3-Alternate conformation bearing bis-bidentate
ligands has been published.
Here, we report on the design, synthesis and characterization
of a series of multivalent ligands based on CA or TCA, in 1,3-
Alternate conformation, bearing four oxamate units (compounds
3
-7, Figure 1).

2
Tetrahedron
2
. Results and discussion
that the replacement of K CO by Cs CO upon the condensation
ACCEPTED MANUSCRIPT
2 3 2 3
of 1 with 24 leads to the formation of the tetraethylester
derivative in 1,3-Alternate conformation. The required compound
The design of the five unprecedented ligands 3-7 (Figure 1) is
based on either p-tert-butylthiacalix[4]arene TCA (3, 5, 7) and p-
tert-butylcalix[4]arene CA (4, 6) backbones in 1,3-Alternate
conformation equipped with four oxamate units. The latter
coordinating groups are connected to the macrocyclic backbone
by (CH ) spacers (n = 2, 3 or 4).
8
was the obtained upon reduction of the tetraethyl ester by
20
LiALH in THF. Unfortunately, this synthetic approach was
only successful with thiacalix[4]arene derivative 8.
4
Compound 9, in 1,3-Alternate conformation, was prepared in
2
n
7
8% yield upon condensation of 8 with the phthalimide
derivative 25 (see experimental section).
Figure 2: Starting compounds 1 and 2, precursors 8-27 used for the
synthesis of ligands 3-7.
Figure 1: p-tert-butylthiacalix[4]arene TCA 1 and p-tert-
butylcalix[4]arene CA 2 in 1,3-Alternate conformation and their derivatives
bearing four oxamate units 3-7.
The phthalimido derivatives 9-13 were converted into their
2
1
amino derivatives 14-18 by hydrazinolysis.
The amino
The synthesis of ligands 3-7 was achieved following a
stepwise strategy. The main intermediate for the synthesis of all
five ligands were the phthalimido derivatives 9-13 in 1,3-
Alternate conformation (Figure 2).
18
compounds 15 and 16 have been already reported and were
obtained in 97% and 98% yield respectively. The other three
amino derivatives 14, 17 and 18 were prepared in 98%, 97% and
9
2% yields respectively (see experimental section).
17
18
The synthesis of phthalimido derivatives 10 and 11 (n = 3,
TCA and CA respectively) has been previously described.
Following the reported procedure, condensation of N-(3-
bromopropyl)phthalimide with the parent TCA 1 or CA 2
The ethyloxamate derivatives 19-23, in the 1,3-Alternate
conformation, were obtained upon condensation of the amino
derivatives 14-18 with ethylchloro(oxo)acetate 27 with yields in
the 63-96% range (see table 1 and experimental section). Finally,
the targeted ligands 3-7 were obtained upon saponification of the
ester derivatives 19-23, with yields in the 85-94% range (see
table 1 and experimental section).
compounds in the presence of Cs CO3 in DMF or Acetone
2
respectively afforded compounds 10 and 11 in 68 and 55% yields
respectively. By applying using the same procedure, compounds
1
2 and 13 (n = 4, TCA and CA respectively) were obtained in
5
0% and 29% yields respectively (see experimental section).
All intermediates and final compounds 3-7, were fully
1
13
characterized in solution by H- and C-NMR spectroscopy, in
addition to other usual technics such as elemental analysis,
melting point and mass spectrometry.
Using the same procedure, the condensation of either
compound 1 or 2 with (2-bromoethyl)phthalimide in the presence
of base, failed to produce intermediates in 1,3-Alternate
conformation, with a shorter spacer (n = 2). It has been
previously reported that, the condensation between TCA 1 and
Table 1: Yields for the condensation of the amino derivatives
4-18 with ethyl chloro(oxo)acetate leading to compounds 19-
3 and their saponification affording the targeted compounds
-7.
(2-bromoethyl)phthalimide in the presence of M CO (M = Na, K
2 3
1
2
3
or Cs) leads to the formation of the mono-substituted derivative
17a
in cone conformation. The same was observed upon increasing
the amount of (2-bromoethyl)phthalimide up to 8 equivalents. In
order to prepare the tetrasubstituted phthalimido compounds
derived from compounds 1 and 2, another previously reported
procedure based on the Mitsunobu reaction was applied. This
strategy requires the coupling of a hydroxy derivative 8 with
Compound
Yield (%)
Compound
Yield (%)
19
76
3
20
68
4
21
67
5
22
63
6
23
96
7
phthalimide 25 in the presence of PPh and DIAD as coupling
agent.
3
94
92
85
87
83
Using K CO3 as base, the synthesis of the tetraethylester
2
19
derivative of CA in cone conformation was reported. We found

3
. Conclusions
added and the reaction mixture was filtered. The white solid thus
ACCEPTED MANUSCRIPT
obtained was washed three times with Et O (3x30 mL). The
2
Five new multivalent ligands based on either p-tert-
white solid was dried under vacuum at 100 °C during 4 hours
butylthiacalix[4]arene 1 or p-tert-butylcalix[4]arene 2 backbones
in 1,3-Alternate conformation bearing four oxamate coordinating
groups at their lower rim were designed. These ligands differ
either by the nature of the calix[4]arene backbone (CA or TCA)
or by the nature of the spacer ((CH ) ) connecting the oxamate
binding units to the backbone. Following a multistep synthesis,
all targeted compounds were prepared in good yields and fully
characterized. The binding propensity of the multivalent ligands
affording the pure product 14 in 1,3-Alternate conformation (1.22
1
g, 98% yield). mp = 254 °C. H-NMR (500 MHz, CDCl , 25 °C):
3
δ(ppm) = 1.27 (36H, s, t-Bu), 2.36 (8H, t, NH -CH ), 3.88 (8H, t,
2
2
13
Ar-O-CH ), 7.34 (8H, s, Ar-H). C-NMR (125 MHz, CDCl , 25
2
3
2
n
°
C): δ = 31.3, 34.3, 41.6, 71.3, 127.8, 128.2, 146.3, 156.7.
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(ethyl-2 oxo-2-
2+
2+
2+
2+
2+
3
-7 towards transition metal such as Ni , Co , Zn , Mn , Cu
aminoacetate)ethoxy]thiacalix[4]arene (19
)
is currently under investigation.
Compound 14 (0.35 g, 0.39 mmol) was dissolved in 20 mL of
CHCl and stirred at 0 °C. Triethylamine (270 ꢀL, 1.95 mmol)
3
dissolved in 10 mL of CHCl and ethyl chloro(oxo)acetate 27
3
4
. Experimental
(
210 ꢀL, 1.95 mmol) dissolved in 10 mL of CHCl were added
3
Materials and methods
dropwise simultaneously and stirred overnight. The solution was
washed four times with H O (4x40 mL). The organic phase was
evaporated to dryness. Compound 19, in 1,3-Alternate
conformation, (0.38 g, 76% yield) was obtained as a white
1
13
2
H-NMR and C-NMR spectra were recorded at room
temperature on Bruker (300, 400 or 500 MHz) NMR
spectrometers.
powder after washing with Et O (10 mL). mp = 166 °C.
2
Mass spectra (ESI) were recorded on a MicroTOF-Q (Bruker)
equipped with an electrospray source.
1
H-NMR (400 MHz, CDCl , 25 °C): δ(ppm) = 1.19 (36H, s, t-
3
Bu), 1.38 (12H, t, CH -CH ), 3.45 (8H, q, NH-CH ), 4.33 (8H, t,
3
2
2
CH -O), 4.35 (8H, q, CH -CH ), 7.52 (8H, s, Ar-H), 8.30 (4H, t,
Microanalyses were performed by the Service de
Microanalyses de la Fédération de Recherche Chimie, Université
de Strasbourg, Strasbourg, France.
2
3
2
13
CH -NH-CO). C-NMR (125 MHz, CDCl , 25 °C): δ(ppm) =
2
3
1
1
4.0, 31.2, 34.2, 39.4, 63.2, 70, 127.3, 132.4, 146.3, 156.7, 157.3,
60.6.
Melting points were measured in capillary on a Stuart
Scientific Melting Point SMP-1 apparatus.
3
+
HRMS
(ESI):
m/z
calcd
for
C H N O S
66 90 5 16 4
3
+
[
M+CH CN+(3H)] : 445.87; found: 445.41. Anal. Calcd. for
3
All reagents were purchased from commercial sources
C H N O S : C, 59.42%, H, 6.54%, N, 4.33%. Found: C,
64
84
4
16 4
4
20
17
18
17b
(
1
including 2, 24-27). The synthesis of 1, 8, 10, 11, 15, and
6
5
9.64%, H, 6.76%, N, 4.21%.
18
has been described in the literature and are not reported here.
All reactions were performed under N atmosphere.
2
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(2 -oxo-2-
aminoacetate)ethoxy]thiacalix[4]arene (3)
Synthesis
KOH (0.105 g, 1.85 mmol) and compound 19 (0.3 g, 0.23
mmol) were dissolved in 20 mL of a THF/H O (1/1) mixture.
2
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis
The mixture was stirred at room temperature overnight. HCl (1N)
was added until pH = 3 was reached and then THF was
evaporated. The solid thus obtained was washed three times with
H O (3x15 mL), twice with CH COCH (2x20 mL) and twice
(
phthalimidoethoxy)thiacalix[4]arene (9)
A mixture of triphenylphosphine (3.80 g, 14.22 mmol)
dissolved in 20 mL of THF and diisopropyl azodicarboxylate
DIAD, 2.90 mL, 14.22 mmol) dissolved in 10 mL of THF was
2
3
3
(
with Et O (2x20 mL) and dried under vacuum at 100 °C during 4
2
stirred at 0 °C for 30 minutes. Phthalimide 25 (2.10 g, 14.22
mmol) was added dropwise and the mixture was further stirred
for 15 minutes. 8 (0.88 mmol) dissolved in 20 mL of THF was
added dropwise and the mixture was stirred for 48 hours at room
temperature. The mixture was evaporated to dryness. Compound
hours. Compound 3 (0.255 g; yield = 94%) in 1,3-Alternate
conformation was obtained as a white powder. mp = 262 °C.
1
H-NMR (500 MHz, DMSO, 25 °C): δ(ppm) = 1.23 (36H, s, t-
Bu), 3.17 (8H, q, NH-CH ), 3.96 (8H, t, CH -O), 7.57 (8H, s, Ar-
2
2
13
H), 8.86 (4H, s, CH -NH-CO). C-NMR (125 MHz, DMSO, 25
2
9
, in 1,3-Alternate conformation, (0.98 g, 78% yield) was
°
C): δ(ppm) = 30.9, 34, 37.8, 66.2, 127.8, 130.2, 146, 156.6,
obtained as a white powder after washing with MeOH (30 mL).
mp = 316 °C
1
58.7, 161.9.
-
-
1
HRMS (ESI): m/z calcd. for C56H N O S [M-H] : 1180.42;
67 4 16 4
H-NMR (500 MHz, CDCl , 25 °C): δ(ppm) = 1.35 (36H, s, t-
3
found: 1179.33. Anal. Calcd. for C H N O S : C, 56.93%, H,
56
68
4
16 4
Bu), 3.83 (8H, t, Phth-CH ), 4.22 (8H, t, CH -O), 7.71 (8H, m,
2
2
13
5.80%, N, 4.74%. Found: C, 56.60%, H, 5.97%, N, 4.50%.
Ar-H), 7.79 (8H, s, Ar-H), 7.87 (8H, m, Ar-H). C-NMR (125
-
1
-1
MHz, CDCl , 25 °C): δ(ppm) = 31.3, 34.5, 36.5, 64.9, 123.3,
UV-vis (CHCl /MeOH (1/1)): λ (nm) / ε (mol Lcm )= 237
3 max
-1
3
1
29, 130.5, 132.2, 133.9, 146.9, 156.9, 167.8.
(20912). IR (cm ): νNH: 3369, 3012 ; νCO :1678
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(ethyl-2-
oxo-2-aminoacetate)propoxy]thiacalix[4]arene (20)
(
aminoethoxy)thiacalix[4]arene (14)
A mixture of 9 (2.00 g, 1.41 mmol) and hydrazine (14.1 mL,
Compound 15 (0.60 g, 0.63 mmol) was dissolved in 20 mL of
2
86 mmol) in 70 mL of EtOH was stirred and refluxed for 24h.
CHCl and stirred at 0 °C. Triethylamine (450 ꢀL, 3.15 mmol)
3
After cooling to room temperature, 150 mL of distilled H O was
dissolved in 10 mL of CHCl and ethylchloro(oxo)acetate 27
2
3

4
Tetrahedron
(
360 ꢀL, 3.15 mmol) dissolved in 10 mL of C
A
H
C
Cl
C
w
E
e
P
re
T
a
E
dd
D
ed MAN
5
U
,11
S
,1
C
7,2
R
3
I
-Tetra-tert-butyl-25,26,27,28-tetrakis
P
T
3
dropwise simultaneously and the mixture was stirred overnight at
(aminobutoxy)thiacalix[4]arene (17)
room temperature. The solution was washed four times with H O
2
A mixture of compound 12 (2.00 g, 1.31 mmol) and hydrazine
14.1 mL, 286 mmol) in 70 mL of EtOH was stirred and refluxed
for 24h. After cooling to room temperature, 150 mL of distilled
H O was added and the reaction mixture was filtrated. The white
(4x40 mL). The organic phase was evaporated to dryness.
(
Compound 20, in 1,3-Alternate conformation, (0.58 g; 68%
1
yield) was obtained as a white powder. mp = 242 °C. H-NMR
2
(
400 MHz, CDCl , 25 °C): δ(ppm) = 1.21 (36H, s, t-Bu), 1.22
3
solid was washed three times with Et O (3x30 mL) and then
2
(
8H, m, CH -CH -CH ), 1.37 (12H, t, CH -CH ), 3.05 (8H, q,
2
2
2
3
2
dried under vacuum at 100 °C during 4 hours, affording the pure
NH-CH ), 3.85 (8H, t, CH -O), 4.43 (8H, q, CH -CH ), 7.32 (8H,
2
2
3
2
13
product 17 (1.27 g, 97% yield) in 1,3-Alternate conformation. mp
s, Ar-H). C-NMR (125 MHz, CDCl , 25 °C): δ(ppm) = 14,
1
3
=
206 °С. H-NMR (300 MHz, CDCl , 25 °C): δ(ppm) = 1.03
3
2
8.8, 31.2, 34.3, 36.3, 63.3, 66, 127.5, 128.1, 146.4, 156.5, 160.7.
+ +
(8H, m, NH
-CH -CH ), 1.23 (8H, m, O-CH -CH ), 1.24 (36H, s,
2 2 2 2 2
HRMS (ESI): m/z calcd. for C H N O S Na [M + Na] :
68
92
4
16 4
t-Bu), 2.53 (8H, t, NH -CH ), 3.81 (8H, t, Ar-O-CH ), 7.28 (8H,
2
2
2
1
6
4
372.73; found: 1371.53. Anal. Calcd. for C H N O S : C,
0.51%, H, 6.87%, N, 4.15%. Found: C, 60.17%, H, 7.00%, N,
.00%.
13
68
92
4
16 4
s, Ar-H). C-NMR (125 MHz, CDCl , 25 °C): δ = 26.4, 30.2,
3
3
1.3, 34.2, 42.3, 68.4, 127.6, 128.1, 145.4, 157.
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(ethyl-2-
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(2-oxo-2-
oxo-2-aminoacetate)butoxy]thiacalix[4]arene (22)
aminoacetate)propoxy]thiacalix[4]arene (5)
Compound 17 (0.25 g, 0.24 mmol) was dissolved in 20 mL of
KOH (0.17 g, 2.96 mmol) and compound 20 (0.5 g, 0.37
CHCl and stirred at 0 °C. Triethylamine (170 ꢀL, 1.24 mmol)
3
mmol) were dissolved in 40 mL of a THF/H O (1/1) mixture.
2
dissolved in 10 mL of CHCl and ethyl chloro(oxo)acetate 27
3
The mixture was stirred at room temperature overnight. HCl (1N)
was added until pH 3 was reached and THF was evaporated. The
white precipitate formed was collected and washed three times
with H O (3x20 mL), twice with CH COCH (2x20 mL) and
(
140 ꢀL, 1.24 mmol) dissolved in 10 mL of CHCl were added
3
dropwise simultaneously and stirred overnight. The solution was
washed four times with H O (4x40 mL). The organic phase was
2
2
3
3
evaporated to dryness. Compound 22 in 1,3-Alternate
twice with Et O (2x20 mL), then dried under vacuum at 100 ° C
2
conformation (0.22 g; 63% yield) was obtained as a white
for 4 hours. Compound 5, in 1,3-Alternate conformation, (0.39 g;
1
1
powder. mp = 242 °C. H-NMR (500 MHz, CDCl
3
, 25 °C):
8
5% yield) was obtained as a white powder. mp = 286 °C. H-
δ(ppm) = 1.13 (8H, m, O-CH -CH -CH -), 1.23 (36H, s, t-Bu),
2
2
2
NMR (400 MHz, DMSO, 25 °C): δ(ppm) = 1.20 (36H, s, t-Bu),
.42 (8H, m, CH -CH -CH ), 3.07 (8H, q, NH-CH ), 3.80 (8H, t,
1
.35 (12H, t, CH -CH ), 1.41 (8H, m, NH-CH -CH ), 3.18 (8H,
3 2 2 2
1
2
2
2
2
13
q, NH-CH ), 3.82 (8H, t, CH -O), 4.32 (8H, q, CH -CH ), 7.15
2 2 3 2
13
CH -O), 7.35 (8H, s, Ar-H), 8.65 (4H, s, CH -NH-CO). C-
2
2
(
8H, s, Ar-H), 7.29 (4H, s, CH -NH-CO). C-NMR (125 MHz,
2
NMR (100 MHz, DMSO, 25 °C): δ(ppm) = 28.7, 30.9, 33.8, 36,
7.8, 127.6, 128.8, 145.4, 156.9, 158.1, 162. HRMS (ESI): m/z
CDCl , 25 °C): δ(ppm) = 14, 25.4, 26.5, 31.4, 34.2, 39.8, 63.2,
3
6
-
-
68.4, 128, 128.2, 145.7, 156.5, 156.9, 160.7. HRMS (ESI): m/z
calcd. for C H N O S [M-H] : 1236.52; found: 1235.4. Anal.
+
+
60
75
4
16 4
calcd. for C H N O S Na [M + Na] : 1428.82; found: 1427.6.
72
100
4
16 4
Calcd. for C H N O S ꢁH O: C, 57.4%, H, 6.26%, N, 4.46%.
60
76
4
16
4
2
Anal. Calcd. for C H N O S : C, 61.51%, H, 7.17%, N,
72
100
4
16 4
Found: C, 57.59%, H, 6.32%, N, 4.38%.
3
.99%. Found: C, 61.21%, H, 7.18%, N, 4.01%.
-
1
-1
UV-vis (CHCl /MeOH (1/1)): λ (nm) / ε (mol Lcm )= 265
21988). IR (cm ): νNH: 3391, 2971; νCO:1664
3
max
-
1
(
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(2-oxo-2-
aminoacetate)butoxy]thiacalix[4]arene (7)
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis
KOH (0.03 g, 0.56 mmol) and compound 22 (0.1 g, 0.07
(
phthalimidobutoxy)thiacalix[4]arene (12)
mmol) were dissolved in 20 mL of a THF/H O (1/1) mixture.
2
1
.5 g (2.31 mmol) of compound 1 and 7.5 g (23.11 mmol) of
The mixture was stirred at room temperature overnight. HCl (1N)
was added until pH 3 was reached and then THF was evaporated.
Cs CO were dissolved in 80 mL of CH COCH and stirred at
2
3
3
3
room temperature for 2h. 5.04 g (23.11 mmol) of N-(4-
bromobutyl)phthalimide 26 was added and the mixture was
stirred for 3 days at 50 °C. After cooling to room temperature, the
reaction mixture was filtrated. The solid thus obtained was
The solid thus obtained was washed three times with H O (3x5
2
mL), twice with CH COCH (2x5 mL) and twice with Et O (2x5
3
3
2
mL) and then dried under vacuum at 100 ° C during 4 hours.
Compound 7 in 1,3-Alternate conformation (0.07 g; 83% yield)
1
washed 3 times with CHCl (3x20 mL). Filtrates were combined
was obtained as a white powder. mp = 246 °C. H-NMR (500
3
and then evaporated affording a yellow oil which was dissolved
MHz, DMSO, 25 °C): δ(ppm) = 1.00 (8H, m, NH-CH -CH ),
2
2
in CHCl (50 mL) and the solution was washed twice with HCl
1.23 (36H, s, t-Bu), 1.31 (8H, m, CH -CH -O), 2.98 (8H, q, NH-
3
2 2
1
N (2x50 mL). The organic phase was evaporated to dryness
CH ), 3.76 (8H, t, CH -O), 7.31 (8H, s, Ar-H), 8.84 (4H, s, CH -
2 2 2
13
leaving a solid which was crystallized from MeOH (100 mL),
NH-CO). C-NMR (125 MHz, DMSO, 25 °C): δ(ppm) = 25.4,
affording the desired compound 12 in 1,3-Alternate conformation
26.2, 31.5, 34.3, 39.2, 68.4, 127.8, 128, 145.9, 156.9, 158.6,
+
+
as a colorless solid (1.75 g, 50 % yield). mp > 320 °С (decomp.).
162.6. HRMS (ESI): m/z calcd. for C H N O S [M] :
64 84 4 16 4
1
H-NMR (500 MHz, CDCl , 25 °C): δ(ppm) = 1.23 (8H, m, Pht-
1293.63; found: 1293.48.Anal. Calcd. for C H N O S : C,
64 84 4 16 4
3
CH -CH ) 1.28 (36H, s, t-Bu), 1.56 (8H, m, CH -CH -CH ), 3.57
57.81%, H, 6.67%, N, 4.21%. Found: C, 58.43%, H, 6.56%, N,
4.13%.
2
2,
2
2
2
(
8H, t, Pht-CH ), 3.9 (8H, t, Ar-O-CH ), 7.34 (8H, s, Ar-H), 7.67
2 2
13
(8H, m, Ar-H), 7.81 (8H, m, Ar-H). C-NMR (125 MHz, CDCl3,
-1
-1
UV-vis (CHCl /MeOH (1/1)): λ (nm) / ε (mol Lcm )= 237
22748). IR (cm ): νNH: 3399, 2974; νCO:1668.
3
max
2
1
5 °C): δ(ppm) = δ = 25.0, 26.3, 31.4, 34.2, 37.7, 68.2, 123.2,
28.3, 132.2, 133.8, 145.8, 157.0, 168.1.
-1
(

5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(ethyl-2-
CH ), 3.71 (8H, s, Ar-CH -Ar), 6.94 (8H, s, Ar-H), 7.7 (8H, m,
ACCEPTED MAN
2
USCRIPT
2
13
oxo-2-aminoacetate)propoxy]calix[4]arene (21)
Ar-H), 7.84 (8H, m, Ar-H). C-NMR (100 MHz, CDCl , 25 °C):
3
δ(ppm) = δ = 25.2, 26.9, 31.7, 33.8, 37.7, 38.6, 70.1, 123.2,
Compound 16 (0.25 g, 0.28mmol) was dissolved in 20 mL of
1
26.3, 132.2, 133.2, 133.8, 143.6, 154.4, 168.2.
CHCl and stirred at 0 °C. Triethylamine (230 ꢀL, 1.7 mmol)
3
dissolved in 10 mL of CHCl and ethylchloro(oxo)acetate 27
3
(
190 ꢀL, 1.7 mmol) dissolved in 10 mL of CHCl were added
3
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis
dropwise simultaneously and stirred overnight. The solution was
washed four times with H O (4x20 mL). The organic phase was
(
aminobutoxy)calix[4]arene (18)
2
evaporated to dryness. Compound 21 in 1,3-Alternate
A mixture of compound 13 (2.00 g, 1.38 mmol) and hydrazine
conformation (0.19 g; 67% yield) was obtained as a white
(14.1 mL, 286 mmol) in 70 mL of EtOH was stirred and refluxed
for 24h. After cooling to room temperature, 150 mL of distilled
powder
AcOEt/Cyclohexane, 1/1). mp = 202 °C. H-NMR (500 MHz,
CDCl , 25 °C): δ(ppm) = 1.21 (8H, m, CH -CH -CH ), 1.24
after
purification
on
a
silica
column
1
(
H O was added and the reaction mixture was filtrated. The white
2
3
2
2
2
solid was washed three times with Et 0 (3x30 mL). The white
2
(
36H, s, t-Bu), 1.37 (12H, t, CH -CH ), 3.06 (8H, q, NH-CH ),
solid was dried under vacuum at 100 °C during 4 hours, affording
3
2
2
3
.34 (8H, t, CH -O), 3.84 (8H, s, Ar-CH -Ar), 4.34 (8H, q, CH -
the pure product 18 (1.19 g, 92% yield) in 1,3-Alternate
2
2
3
13
1
CH ), 6.98 (8H, s, Ar-H), 7.06 (4H, t, CH -NH-CO). C-NMR
conformation. mp > 206 °С (decomp.). H-NMR (500 MHz,
2
2
(
125 MHz, CDCl , 25 °C): δ(ppm) = 14, 29.3, 31.6, 33.9, 36.9,
CDCl , 25 °C): δ(ppm) = 1.22 (8H, m, NH -CH -CH ), 1.26
3
3
2
2
2
3
9.2, 63.2, 67.5, 125.6, 133.1, 144.4, 154.5, 156.5, 160.7. HRMS
(36H, s, t-Bu), 1.3 (8H, m, O-CH -CH ) 2.60 (8H, t, NH -CH ),
2 2 2 2
+
+
(ESI): m/z calcd. for C H N O Na [M + Na] : 1300.56;
3.41 (8H, t, Ar-O-CH ), 3.73 (8H, s, Ar-CH Ar), 6.94 (8H, s, Ar-
72
100
4
16
2
2-
13
found: 1299.69. Anal. Calcd. for C H N O : C, 67.69%, H,
H). C-NMR (125 MHz, CDCl , 25 °C): δ = 27.1, 30.4, 31.6,
72
100
4
16
3
7
.89%, N, 4.39%. Found: C, 67.41%, H, 7.95%, N, 4.33%.
33.8, 38.9, 42.3, 70.4, 125.9, 133, 143.4, 154.6.
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(2-oxo-2-
aminoacetate)propoxy]calix[4]arene (4)
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(ethyl-2-
KOH (0.07 g, 1.2 mmol) and compound 21 (0.2 g, 0.15 mmol)
oxo-2-aminoacetate)butoxy]calix[4]arene (23)
were dissolved in 40 mL of a THF/H O (1/1) mixture. The
mixture was stirred at room temperature overnight. HCl (1N) was
added until pH 3 was reached and then THF was evaporated. The
2
Compound 18 (0.65 g, 0.69 mmol) was dissolved in 30 mL of
CHCl and stirred at 0 °C. Triethylamine (500 ꢀL, 3.63 mmol)
3
dissolved in 10 mL of CHCl and ethyl chloro(oxo)acetate 27
3
solid thus obtained was washed three times with H O (3x20 mL),
2
(
400 ꢀL, 3.56 mmol) dissolved in 10 mL of CHCl were added
3
twice with CH COCH (2x20 mL) and twice with Et 0 (2x20
3
3
2
dropwise simultaneously and stirred overnight. The solution was
mL), then dried under vacuum at 100 ° C during 4 hours.
washed four times with H O (4x30 mL). The organic phase was
2
Compound 4 in 1,3-Alternate conformation (0.16 g; 92% yield)
1
evaporated to dryness. Compound 23 in 1,3-Alternate
was obtained as a white powder. mp > 320 °С (decomp.). H-
conformation (0.89 g; 96% yield) was obtained as a white
NMR (300 MHz, DMSO, 25 °C): δ(ppm) = 1.18 (36H, s, t-Bu),
1
powder. mp = 212 °C. H-NMR (500 MHz, CDCl , 25 °C):
3
1
.58 (8H, m, CH -CH -CH ), 3.1 (8H, q, NH-CH ), 3.39 (8H, t,
2 2 2 2
δ(ppm) = 1.22 (8H, m, O-CH -CH -CH ), 1.25 (36H, s, t-Bu),
2
2
2
CH -O), 3.62 (8H, s, Ar-CH -Ar), 6.95 (8H, s, Ar-H), 8.69 (4H,
2
2
13
1.38 (12H, t, CH -CH ), 1.43 (8H, m, NH-CH -CH ), 3.24 (8H,
3 2 2 2
s, CH -NH-CO). C-NMR (125 MHz, DMSO, 25 °C): δ(ppm) =
2
q, NH-CH ), 3.36 (8H, t, CH -O), 3.75 (8H, s, Ar-CH Ar), 4.33
2
2
2-
2
1
9.4, 31.4, 33.4, 36.1, 37.6, 69.0, 126.3, 132.5, 142.5, 154.2,
58.5, 162.1. HRMS (ESI): m/z calcd. for C H N O Na [M +
(
8H, q, CH -CH ), 6.94 (4H, s, CH -NH-CO), 7.2 (8H, s, Ar-
3 2 2
13
64
86
4
16
+
H). C-NMR (125 MHz, CDCl , 25 °C): δ(ppm) = 14, 25.6, 27,
3
Na] : 1187.56; found: 1188.35. Anal. Calcd. for C H N O : C,
64
86
4
16
3
1
1.6, 33.8, 38.9, 39.9, 63.2, 70.0, 126.0, 133.1, 143.8, 154.5,
6
4
5.85%, H, 7.43%, N, 4.80%. Found: C, 65.23%, H, 7.48%, N,
.79%.
+
56.6, 160.7. HRMS (ESI): m/z calcd. for C H N O Na [M +
76
108
4
16
+
Na] : 1356.69; found: 1355.77. Anal. Calcd. for C H N O : C,
76
108
4
16
-
1
-1
UV-vis (CHCl /MeOH (1/1)): λ (nm) / ε (mol Lcm )= 236
23640). IR (cm ): νNH: 3388, 2973; νCO:1662.
68.44%, H, 8.16%, N, 4.20%. Found: C, 68.14%, H, 8.22%, N,
4.11%.
3
max
-
1
(
5
,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis
5,11,17,23-Tetra-tert-butyl-25,26,27,28-tetrakis-[(2-oxo-2-
aminoacetate)butoxy]calix[4]arene (6)
(
phthalimidobutoxy)calix[4]arene (13)
3
g (4.53 mmol) of compound 2 and 15 g (45.11 mmol) of
KOH (0.14 g, 2.39 mmol) and compound 23 (0.4 g, 0.29
Cs CO were dissolved in 120 mL of DMF and stirred at room
mmol) were dissolved in 40 mL of a THF/H O (1/1) mixture.
2
3
2
temperature for 2h. 13g (45.15 mmol) of N-(4-
bromobutyl)phthalimide 26 was added and the mixture was
stirred at 50 °C for 3 days. After cooling to room temperature, the
reaction mixture was filtrated. The solid thus obtained was
The mixture was stirred at room temperature overnight. HCl (1N)
was added until pH 3 was reached and then THF was evaporated.
The solid thus obtained was washed three times with H O (3x20
2
mL), twice with CH COCH (2x20 mL) and twice with Et O
3
3
2
washed 3 times with CHCl (3x20 mL). Filtrates were combined
(2x20 mL), then dried under vacuum at 100 °C during 4 hours.
3
and the evaporated leading to a yellow oil which was dissolved in
Compound 6 in 1,3-Alternate conformation (0.30 g; 87% yield)
1
CHCl (100 mL) and the solution was washed twice with HCl 1N
was obtained as a white powder. mp > 248 °С (decomp.). H-
3
(2x100 mL). The organic phase was evaporated to dryness
NMR (500 MHz, DMSO, 25 °C): δ(ppm) = 1.20 (36H, s, t-Bu),
1.22 (8H, m, NH-CH -CH ), 1.38 (8H, m, CH -CH -O), 3.05
leaving a solid which was crystallized from a CHCl /MeOH 2/20
3
2
2
2
2
mixture (40 mL), affording the desired compound 13 in 1,3-
(8H, q, NH-CH ), 3.33 (8H, t, CH -O), 3.67 (8H, s, Ar-CH Ar),
2
2
2-
13
Alternate conformation as a white powder (1.9 g, 29 % yield).
6.93 (8H, s, Ar-H), 8.78 (4H, s, CH -NH-CO). C-NMR (125
2
1
mp > 244 °С (decomp.). H-NMR (400 MHz, CDCl , 25 °C):
MHz, DMSO, 25 °C): δ(ppm) = 25.1, 26.4, 31.4, 33.4, 37.8, 38.7,
3
δ(ppm) = 1.22 (36H, s, t-Bu), 1.38 (8H, m, Pht-CH -CH ), 1.61
69.8, 125.8, 132.7, 142.5, 154.1, 158.1, 162.1. HRMS (ESI): m/z
2
2,
-
(
8H, m, CH -CH -O), 3.45 (8H, t, Pht-CH ), 3.61 (8H, t, Ar-O-
calcd. for C H N O [M-H] : 1220.48; found: 1219.64. Anal.
2
2
2
68 91
4
16

6
Tetrahedron
%. MANUSCRIPT
Calcd. for C H N O : C, 66.86%, H, 7
A
.59
C
%
C
,
E
N,PT4.5
ED
9
68
92
4
16
Found: C, 66.44%, H, 7.67% N, 4.64%.
Ovsyannikov, A.; Ferlay, S.; Solovieva, S. E.; Antipin, I. S.;
Konovalov, A. I.; Kyritsakas, N.; Hosseini, M. W. Dalton Trans.,
2013, 9946-9953; (d) Ovsyannikov, A.; Ferlay, S.; S. E.
Solovieva, I. S. Antipin, A. I. Konovalov, N. Kyritsakas and M.
W. Hosseini Inorg. Chem. 2013, 52, 6776; (e) Ovsyannikov, A.;
Ferlay, S.; Solovieva, S. E.; Antipin, I. S.; Konovalov, A. I.;
Kyritsakas, N.; Hosseini, M. W. Dalton Trans., 2014, 43, 158-
-
1
-1
UV-vis (CHCl /MeOH (1/1)): λ (nm) / ε (mol Lcm )= 236
20164). IR (cm ): νNH: 3393, 2970; νCO:1671.
3
max
-
1
(
Acknowledgements
1
65; (f) Ovsyannikov, A.; Ferlay, S.; Solovieva, S. E.; Antipin, I.
S., Konovalov, A. I.; Kyritsakas, N.; Hosseini, M. W.
Macroheterocycles, 2015, 8, 113-119.
9. Ovsyannikov, A. S.; Noamane, M. H.; Abidi, R.; Ferlay, S.;
Solovieva, S. E.; Antipin, I. S.; Konovalov, A. I.; Kyritsakas,
We thank the University of Strasbourg, the C.N.R.S, the
International centre for Frontier Research in Chemistry (icFRC),
the Labex CSC (ANR-10-LABX- 0026 CSC) within the
Investissement d’Avenir program ANR-10-IDEX-0002-02, the
Institut Universitaire de France, the Ministère de l’Enseignement
Supérieur et de la Recherche for financial support and the
Tunisian government for a PhD fellowship to M. H. N.
N.; Hosseini, M. W. CrystEngComm
0. (a) Mourer, M.; Regnouf-de-Vains, J-B. Tet. Lett., 2006, 47, 1895-
899; (b) Casnati, A.; Baldini, L. ; Sansone, F.; Ungaro, R.;
, 2016, 18, 691-703.
1
1
Armaroli, N.; Pompei, D.; Barigelletti, F. Supramol. Chem., 2002,
14, 281-289.
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1. (a) Akdas, H.; Graf, E.; Hosseini, M. W.; De Cian, A.;
Harrowfield, J. McB. Chem. Commun., 2000, 2219-2220; (b)
Dalgarno, S. J.; Claudio-Bosque, K. M.; Warren, J. E.; Glass, T.
E.; Atwood, J. L. Chem. Commun., 2008, 1410-1411; (c) Liu, Y-
J. ; Huang, J-S.; Chui, S. S-Y.; Li, C-H.; Zuo, J-L.; Zhu, N.; Che,
C-M. Inorg. Chem. 2008, 47, 11514-11518; (d) Park, K-M. ; Lee,
E.; Park, C. S.; Lee, S. S. Inorg. Chem., 2011, 50, 12085-12090;
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