The design and synthesis of acrylato and imino derivatives of calix[4]arene for applications in static and dynamic combinatorial libraries

Article abstract of DOI:10.3184/030823410X12627159407690

The synthesis of novel calix[4]arene tetra-acrylates and the potential use of macrocyclic platforms in the development of static and dynamic combinatorial libraries (DCL) using reversible imine formationare described. Using such a macrocyclic platform in DCL formation results in a large number of library members while keeping the number of building blocks in the library to a minimum number.

Full text of DOI:10.3184/030823410X12627159407690

JOURNAL OF CHEMICAL RESEARCH 2010
RESEARCH PAPER 61
FEBRUARY, 61–67
The design and synthesis of acrylato and imino derivatives of
calix[4]arene for applications in static and dynamic combinatorial
libraries
Adam Le-Gresleya,b* and Nikolai Kuhnerta,c
aFaculty of Health and Medicinal Sciences, University of Surrey, Guildford, Surrey GU2 7XH, UK
bPresent address: Pharmacy and Chemistry, Kingston University, Kingston-upon-Thames, Surrey KT1 2EE, UK
cPresent address: School of Engineering and Science, Jacobs University Bremen, Campusring 8, 28759 Bremen, Germany
The synthesis of novel calix[4]arene tetra-acrylates and the potential use of macrocyclic platforms in the develop-
ment of static and dynamic combinatorial libraries (DCL) using reversible imine formationare described. Using such
a macrocyclic platform in DCL formation results in a large number of library members while keeping the number of
building blocks in the library to a minimum number.
Keywords: calixarenes, supramolecular chemistry, host–guest systems, self-assembly
carbonyl and an olefinic moiety, which must be considered as
the two synthetically most versatile functional groups in
organic chemistry, were chosen to allow a maximum scope and
versatility for further functionalisations.
We have recently reported the use of calix[4]arene macrocy-
cles as useful platforms for the development of static and
dynamic macrocyclic libraries.1,2 A synthetic receptor should
bind to a given guest with a high binding constant and
high selectivity. The binding sites for the receptor need to be
identified efficiently, necessitating the development of novel
combinatorial methodology for the synthesis of libraries of
macrocycles.3,4 This methodology can either be directed
towards the generation of static libraries.5,6 or towards dynamic
combinatorial libraries (DCL) as proposed by Lehn, Sanders
and co-workers.7–13 For the development of static combinato-
rial libraries, reactions and reaction conditions need to be iden-
tified that are reliable, tolerate a wide variety of chemically
diverse building blocks and yield products in good yields.
Achieving this target is notoriously difficult in macrocyclic
chemistry with multiple reaction products frequently possible
and with the requirement for multiple functional group trans-
formations to be achieved in a single synthetic operation. For a
DCL, reactions need to be identified that are reversible and
allow, in the presence of a guest, a shift of the distribution of
possible reaction products by establishing a new equilibrium
involving guest molecule and product. When designing such a
dynamic combinatorial library we would like to argue that it
might be beneficial to obtain a maximum number of compo-
nents of the library while using a minimum amount of building
blocks. With this concept a larger number of possible library
members can be generated in a single step and an optimisation
of the chemical space covered by the DCL can be achieved. In
this paper, we report the expansion of this novel approach. By
modifying the upper rim of a calix[4]arene with several func-
tionalities suitable for further derivatisation, we can utilise a
reversible reaction with a series of structurally diverse reagents
suitable for static and dynamic libraries. We communicated
our success in developing imine libraries and carcerands ear-
lier.1,2 Furthermore, a series of static cyclopeptide macrocyclic
libraries have been reported.14–17
The coupling proceeded as expected to give the novel deep
cavity calix[4]arenes 2–4 and 6 in good yields as the all-trans
isomers, 5 and 7 having been reported earlier (see Table 1).1
All spectroscopic data were in full agreement with the struc-
ture. The 1H NMR chemical shifts of the calix[4]arene methy-
lene protons provided evidence for the deep cavity nature of
the compounds.18,19
For example, the 1H NMR spectrum for 4 (see Fig. 1) clearly
shows the β-trans olefinic protons and the well-separated
methylene signals at 3.2 ppm and 4.4 ppm, which are charac-
teristic of a cone conformational structure.
With a view to chiral recognition, the synthesis of an enan-
tiomerically pure deep cavity calix[4]arene was attempted.
The acrylate derived from L-menthol was synthesised and sub-
sequently coupled to the tetraiodocalix[4]arene. The desired
target compound was obtained after reactions over a period of
150h in 40% yield using Pd(OAc)2/DPPP (10%) in DMF with
Et3N. An inspection of the 1H NMR spectra of the crude reac-
tion mixture over the reaction time suggests rapid formation
(64h) of a mixture in which the triolefinic calixarene predomi-
nates and there is a comparatively slow (86h) progression of
the reaction to the tetra-olefinic product 6.
Ungaro and co-workers have shown that, in the case of
L-alanine substituted broader rim calix[4]arenes, a stereogenic
centre close to the aromatic calix[4]arene protons gives rise
to non equivalent aromatic protons.20 In our system, the two
aromatic protons are diastereotopic, with the aromatic rings of
the calixarene acting as a stereogenic plane, similar to the ala-
nine derivatives of Ungaro. This is supported by the 13C NMR
spectrum for 6, which shows additional aromatic signals at
around 130ppm. This effect is solvent independent and, in the
1
case of 6 the two H NMR aromatic signals (shown in Fig. 2
at 6.89ppm and 6.80ppm) were observed in both CDCl3 and
d6-DMSO. This observation is rather surprising since the
stereogenic centre of the menthol residue is separated from the
stereogenic aromatic ring by eight chemical bonds.
Results and discussion
Synthesis of static libraries
With the aim of enhancing our novel synthetic methodology
for macrocyclic library synthesis we used Heck coupling to
obtain the deep cavity calix[4]arene acrylates 2, 3, 4, 5, 6 and
7 from tetraiodo compound 1 and the corresponding acrylate
using palladium acetate and 1,3-bis-(diphenylphosphino)prop
ane as a coligand (Scheme 1).18 Acrylates comprising both a
The next stage involved the reaction of 5 to give tetracon-
densation products 8–22 (see Scheme 2). A range of amines
were selected to demonstrate the scope of this approach for the
formation of a static combinatorial library and included amines
comprising of electron rich/deficient aromatic systems and
amines possessing hydrogen bonding acceptors and donors
e.g. e, k, l and m. Imine formation was carried out with an
excess of eight equivalents of the amine in chloroform in the
presence of molecular sieves.
* Correspondent. E-mail: a.legresley@kingston.ac.uk

62 JOURNAL OF CHEMICAL RESEARCH 2010
Scheme 1
Table 1 Selected data on the acrylate coupling reactions
Dynamic combinatorial library
After the successful synthesis of a static imine library, we con-
sidered a dynamic library based on the imine condensation
reaction of tetra-formyl compound 5. Imine formation is a
reversible reaction therefore allowing the exploitation of ther-
modynamic control in a highly modular approach. The two
basic advantages of using a macrocyclic scaffold in a DCL
should be emphasised here. Firstly the macrocyclic scaffold
presents a pre-formed binding site for the potential guest hence
making the host guest interactions entropically favourable.
Secondly, and more importantly, the use of a macrocyclic
scaffold allows the maximisation of possible reaction products
while using a minimum of building blocks and required
reaction steps. Additionally, the four amine building blocks
used are unable to react with themselves allowing selectivity
advantages in the library. We have only used achiral amines.
Acrylate
Yield/ %
Reaction
time/ h
1H NMR chemical shift
calix[4]arene ArH/ ppm
2
3
4
5
6
7
68
50
75
73
40
32
24
48
48
36
150
12
6.92
6.85
6.93
6.93
6.87 and 6.76
6.93
The tetra-imines (with the exception of 11, 18, 19 and 20,
which could not be synthesised) were obtained in moderate
to good yields and displayed the expected C4V symmetry
along with the expected, spectroscopic data, supporting their
structures (see Table 2).
Fig. 1 1H NMR spectrum of 4 (270MHz, CDCl3, 25 ºC). Broad signals are characteristic of anisotropy associated with slow tumbling
of calixarene.16

JOURNAL OF CHEMICAL RESEARCH 2010 63
Table 2 Yields and selected spectroscopic data for tetra-
imines 8–22
Tetra- Amine Yield/ Reaction 1H NMR chemical LSIMS
imine
%
time/ h shift N = CH/ ppm m/z
8
9
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
75
72
68
–
59
83
77
75
45
38
–
10
11
10
–
12
7
11
10
12
15
–
8.19
8.16
8.17
–
7.90
8.05
8.06
8.06
8.01
8.01
–
1768
1646
1703
–
1917
1502
1564
1792
2162
1856
–
10
11
12
13
14
15
16
17
18
19
20
21
22
–
–
78
49
–
–
10
8
–
–
8.12
8.02
–
–
1663
1671
In a DCL, the potential number of unique calix[4]arene com-
pounds possible when 5 is reacted with four different amines
could comprise 158 different imines in the cone conformation
(including mono-, di-, tri- and tetra-imines, regioisomers and
possible stereoisomers).
The inclusion of an additional amine adds another 133 possi-
ble permutations of imine reaction products to the dynamic
library, clearly illustrating the immense diversity covered with
our approach. The possibility of exerting thermodynamic con-
trol via a guest and the subsequent predominance of one (or
significantly fewer than 158) compounds would certainly illus-
trate the potential value of the method described. If compared
to a chemical library comprising four amino acid building
blocks, which comprises a maximum number of 120 members
Fig. 2 The aromatic region of the 1H NMR spectrum of 6 (CDCl3
referenced to solvent, 270MHz, 298K).
However, combination of the inherent stereoisomerism of the
calix with the imine permutations possible with a single race-
mic amine add an additional 157 possible stereoisomers to the
library. Therefore such a DCL composed of a macrocyclic
scaffold and additional building blocks cover a large range of
chemical space.
Scheme 2

64 JOURNAL OF CHEMICAL RESEARCH 2010
Fig. 3 Scheme showing tentative major product imines formed (as judged by the intensities of peaks in LSIMS mass spectra) in
the presence and absence of a guest molecule.
(70 cyclic tetrapeptides + 40 tripeptides + 10 dipeptides) the
advantage of using a macrocyclic scaffold becomes evident.
A representative example of this thermodynamic preference
was given by LSIMS–MS analysis of the products, when 5 was
mixed with stoichiometric (4:1 amine/calixarene) amounts of
amines 5a, 5c, 5e and 5g. After 12 h reaction time a statistical
mixture of at least 30 imines with distinct m/z values (as judged
by the intensity of the molecular ions in the LSIMS-MS) was
observed (See Table 3). After a prolonged reaction time of 64
h, there was strong evidence for equilibration under thermody-
namic control as illustrated by the predominance of a hetero-
condensation product 5c (m/z 1434) with smaller amounts of
5a, 5ae and 5g as judged by the relative intensities of the
molecular ions in the LSIMS-MS. Longer reaction times did
not change the composition of the DCL significantly.
It cannot be excluded that one of the amines acts as a
templating guest to induce the formation of the four most
stable tetra-imines. As a control experiment we added two
non-amine templates (barbituric acid 23 and biotin 24) to the
dynamic library described above. Again LSIMS-MS allowed
us to identify the major components of the library after 48 h of
equilibration.
FAB-MS spectra of representative equimolar mixtures
of imines revealed differences of relative intensities of the
molecular ions within 20%, indicating that LSIMS-MS is in
this case a valid technique for the analysis of structurally
closely related compounds of comparable molecular weight.21
It is furthermore worth noting that the library components
could not be sufficiently resolved by HPLC.
The highest intensity molecular ion when barbituric acid
was present corresponds to 5e with a complete loss of the
signal for 5c. In the case of biotin the highest intensity mole-
cular ion corresponds to the tris-imine 5cgg.21 Note that in
such a mass spectrometry experiment, the relative intensities
of the individual molecular ions are not necessarily a reliable
indication of the amount of product formed. However, the
experiments presented clearly demonstrate that upon addition
of a template guest the composition of the library changes
dramatically.
Table 3 Masses and molecular formulas for DCL products
Imine
Molecular
formula
Mass peak Intensity/
Guest
m/z
relative %
5c
5ae
5a
5e
5e
5cgg
C91H87O15N
C101H96O15N3
C91H87O16N
C H O N
1434
1590
1450
1487
1487
1540
35
15
10
5
39
25
None
None
None
None
23
C94H90O15N22
84 90 15
C H O13N3
24
99 105
stereoisomers. All attempts to purify the major library compo-
nent for more detailed binding studies unfortunately failed.
Additional evidence for binding of the guest template to a
component of the dynamic library comes from diffusion NMR
experiments, indicating a reduced diffusion coefficient of bar-
bituric acid and biotin benzyl ammonium salt in the presence
of the dynamic library as opposed to the templates in the
absence of the dynamic library.1
These experiments clearly indicated that when alternative
guest templates were introduced to the dynamic library a new
equilibrium is established where a thermodynamically more
stable host–guest system results in molecular amplification of
individual DCL members.
Conclusion
We have demonstrated the ready availability of a series of
multi-functionalised macrocyclic species using reliable Heck
chemistry. Furthermore we have shown that acrylato-aldehyde
substituted calix[4]arenes can be further elaborated into more
complex tetra-imine derivatives.Acrylato-aldehyde substituted
calix[4]arenes can engage in thermodynamically controlled,
reversible reactions with primary amines. Through introduc-
tion of four different amines it is statistically possible to
form 158 different permutations of mono, di, tri, and tetra
functionalised calix[4]arene, yet in our case comparatively few
were observed, thereby covering a large amount of chemical
space with a minimum number of building blocks. As a proof
of principle it was shown that the DCL composed of a macro-
cyclic scaffold and four amine building blocks induces a new
thermodynamic equilibrium by addition of template guest
molecules.
Hence these experiments provide a clear proof of concept of
these macrocyclic DCLs. The 1H NMR spectra of the dynamic
library support the formation of a major mono-imine 5e and
tris-imine 5ccg, respectively. The DCL product 5cgg exists as
three possible isomers (regioisomers and enantiomeric stereo-
isomers) and 5ae as two possible regioisomers. From the
NMR data obtained it is currently not possible to distinguish
and unambiguously assign the structure of the major regio/
Experimental
1H and 13C NMR spectra were recorded on either a JEOL 270MHz,
Bruker AC 300MHz or a DRX 500MHz spectrometer. Standard

JOURNAL OF CHEMICAL RESEARCH 2010 65
Bruker 2-D software was used for spectral processing. All coupling
constants are quoted in Hz. Elemental analysis were made on a
Leeman Labs CE440 Elemental Analyzer. Note that solvent inclusion
complexes of calix[4]arenes often influence elemental analysis and
this is taken into account for each compound.22,23 IR spectra were
determined on a Perkin Elmer 200 Spectrometer. The mass spectra
(m/z) were recorded either by the EPSRC National Mass Spectrome-
try Service Centre, Swansea or a ThermoFinnigan Mat 95 X. All
LSIMS data were collected on a ThermoFinnigan Mat 95 X and
ESI-MS was recorded on a ThermoFinnigan DECA CQXP Plus.
Acrylates were synthesised according to a general experimental shown
below. All other chemicals/reagents were purchased from the Aldrich
Chemical Company and used without further purification unless stated
otherwise. Solvents were dried and purified according to standard
procedures. Melting points were determined on a Kofler hot-stage
apparatus and are uncorrected. All compounds are named using the
simplified IUPAC calixarene nomenclature.
H, ArH), 6.93 (s, 8 H, ArH), 6.32 (d, 3JH,H = 16.0 Hz, 4 H, Ar-CH=CH–
C=O), 4.43 (d, 2JH,H = 13.4 Hz, 4 H, CHAH Ar), 3.93 (t, 3JH,H = 6.4 Hz,
8 H, CH2O), 3.19 (d, JH,H = 13.4 Hz, 4 HB, CHAHBAr), 1.90 (m, 8 H,
2
3
CH CH O), 1.50–1.40 (m, 8 H, OCHCH2CH2), 1.00 (t, JH,H = J 8.3
Hz,2 122 H, CH3CH2)ppm. 13C NMR (100 MHz; CDCl , 25 °C):
δ = 165.6, 159.0, 150.8, 146.4, 135.4, 129.8, 129.2, 1293.0, 125.9,
122.1, 115.7, 75.6, 32.5, 31.3, 19.5, 14.2 ppm. m/z (EI) 1232 [M+].
Found C, 77.65; H, 6.21% C80H80O requires C, 77.90; H, 6.54%.
5,11,17,23-Tetrakis[(E)-2-(4-ca1r2boxyphenoxy)ethenyl]-25,26,27,
28-tetrapropoxycalix[4]arene (5): M.p. 94–96 °C. IR (Nujol)/cm−1:
1730 (C=O), 1720 (C=O), 1631 (C=C); 1H NMR (270 MHz; CDCl3,
25 °C): δ = 9.81 (s, 4 H, CHO), 7.69–7.64 (m, 8 H, ArH, Ar-CH=),
7.59 (s,4 H, ArH), 7.41–7.35 (m, 8 H, ArH), 6.93 (s, 8 H, ArH), 6.34
3
2
(d, JH,H = 15.6 Hz, 4 H, CH–C=O), 4.51 (d, JH,H = 13.8 Hz, 4 H,
CH H Ar), 3.93 (t, 3JH,H = 6.9 Hz, 8 H, OCH2CH2), 3.28 (d, 2J = 13.8
Hz,A4 BH, CHAHBAr), 1.98–1.91 (m, 8 H, OCH2CH2CH3)H,,H1.07 (t,
3JH,H = 8.3 Hz, 12 H, CH CH ) ppm. 13C NMR (100 MHz; CDCl3,
25 °C): δ = 191.3, 165.4, 31512.4, 147.3, 137.6, 135.7, 129.9, 128.9,
128.7, 128.5, 128.1, 126.6, 123.2, 114.6, 77.2, 31.0, 23.4, 10.3 ppm.
m/z (LSIMS) 1289 [M+]; Found C, 69.94; H 5.58% C80H72O16 · 4H2O
requires C, 70.57; H, 5.92%.
General procedure for preparation of acrylates
K CO3 (0.89 g, 6.45 mmol) and the alcohol (6.40 mmol) were stirred
in2 DCM (75 mL) for 10min at room temperature. Acryloyl chloride
(0.52 mL) was slowly added with the room temperature being main-
tained. Upon completion of the reaction, it was quenched with water
(200mL0 and the organic component extracted with DCM (3 × 50
mL). The combined organic extracts were washed with HCl (3 × 20
mL 3M), water (2 × 50 mL) NaOH (3 × 30 mL, 2M) and again with
water (2 × 50 mL). The organic extract was dried (Na2SO ), filtered
and evaporated under reduced pressure. Solid acrylates4 could be
recrystallised from methanol/diethyl ether and all acrylates were
stored below 0ºC or used immediately.
5,11,17,23-Tetrakis[(E)-2-(L-menthoxycarbonyl)ethenyl]-25,26,
27,28-tetrabutoxycalix[4]arene (6): M.p. 85–87 °C. IR (Nujol)/cm−1:
1708 (C=O), 1634 (C=C); 1H NMR (270 MHz; CDCl3, 25 ºC):
δ = 7.35 (d, 3JH,H = 16.2 Hz, 4 H, Ar-CH=), 6.87(s, 4 H, ArH) 6.76 (s,
3
4 H, ArH) 6.12 (d, JH,H = 16.2 Hz, 4 H, CH–C=O), 4.65 (m, 4 H,
CHOC=O) 4.43 (d, 2JH,H = 13.4 Hz, 4 H, CH H Ar), 3.93 (t, 3JH,H = 6.4
Hz, 8 H, CH2O), 3.19 (d, 3JH,H = 13.4 Hz, 4AH,BCH H Ar), 1.90 (m, 8
H, CH2CH2O), 1.67–1.60 (m, 12 H, OCHCH2CH aAndBOCHCH) 1.50–
1.40 (m, 8 H, OCHCH2CH2 ), 1.00 (t, 3JH,H = 8.3 Hz, 12 H, CH3CH2)
0.98–0.78 (m, 60 H, (CH3)2CH and CH CH2CHCH3) ppm. 13C NMR
(100 MHz; CDCl3, 25 °C): δ = 166.7,2 158.4, 144.4, 135.2, 130.2,
129.2, 127.5, 116.7, 75.1, 73.8, 47.4, 40.9, 34.4, 32.2, 31.4, 31.3, 30.9,
26.4, 22.1, 20.9, 19.3, 16.4, 14.1 ppm. m/z (EI) 1482 [M+]. Found C,
General procedure for preparation of 2–7
Triethylamine (0.215 mL, 0.156 g, 1.54 mmol) and acrylate (1.54
mmol) were added to a stirred solution of 5,11,17,23-tetraiodocalix-
arene-25,26,27,28-tetra-n-butylether (0.3 g, 0.27 mmol) 1 in DMF (40
mL). After 10 minutes vigorous stirring at 25 °C palladium acetate
(0.006 g, 0.027 mmol) and 1,3-bis(diphenylphosphinopropane) (0.027
g, 0.027 mmol) were added and the mixture heated to 90 °C and
stirred for 12–150 h. After addition of diethyl ether (100 mL) the mix-
ture was washed with HCl (3 × 20 mL 3M). The organic extract was
dried (Na2SO4), filtered and evaporated under reduced pressure.
The residue was further dried in a desiccator (SiO2) under reduced
pressure for 12 h and recrystallised from methanol to give the
calix[4]arene 2–7.
72.40; H, 9.00% C96H136
O · 6H2O requires C, 72.51; H, 9.38%.
5,11,17,23-Tetrakis[(E1)2-2-(4-carboxyphenoxycarbonyl)ethenyl]-
25,26,27,28-tetrabutoxycalix[4]arene (7): M.p. 103–105 °C. IR
(Nujol)/cm−1: 1748 (C=O (ester)), 1710 (C=O), 1615 (C=C); 1H NMR
(270 MHz; CDCl3, 25 °C): δ = 9.99 (s, 4 H, CHO), 7.79 (d, 3JH,H = 8.6
3
Hz, 8 H, ArH (benzenaldehyde)), 7.62 (d, JH,H = 15.9 Hz, 4 H, Ar-
CH=), 7.28 (d, 3JH,3H = 8.6 Hz, 8 H, ArH (benzenaldehyde)), 6.93 (s, 8
H, ArH) 6.37 (d, JH,H = 15.9 Hz, 4 H, Ar-CH=CH–C=O), 4.50 (d,
2JH,H = 13.2 Hz, 4 H, CH HBAr), 3.97 (t, 3JH,H = 6.4 Hz, 8 H, CH O),
3.19 (d, JH,H = 13.2 Hz, A4 H, CHAHBAr), 1.90 (m, 8 H, CH2CH22O),
2
3
5,11,17,23-Tetrakis[(E)-2-(p-tert-butylphenoxycarbonyl)ethenyl]-
25,26,27,28-tetrabutoxycalix[4]arene (2): M.p. 144–147 °C. IR
(Nujol)/cm−1: 1732 (C=O), 1620 (C=C). 1H NMR (270 MHz; CDCl ,
25 °C): δ = 7.58 (d, 3JH,H = 16.0 Hz, 4 H, Ar-CH=), 7.29 (d, 3JH,H = 8.37
1.50–1.35 (m, 8 H, OCHCH2CH2 ), 1.00 (t, JH,H = 8.3 Hz, 12 H,
CH3CH2) ppm. 13C NMR (100 MHz; CDCl3, 25 °C): δ = 191.5, 165.4,
156.1, 147.2, 142.3, 136.0, 131.7, 131.3, 129.7, 128.8, 123.1, 114.8,
75.6, 32.5, 31.2, 19.7, 14.3 ppm. m/z (EI) 1345[M+]. Found C, 68.97;
H, 5.92% C84H80O16 · 6H2O requires C, 69.41; H, 6.38%.
3
Hz, 8 H, ArH), 7.01 (d, JH,H = 8.7 Hz, 8 H, ArH), 6.92 (s, 8 H,
3
ArH(calix)), 6.32 (d, JH,H = 16.0 Hz, 4 H, CH–C=O), 4.41 (d,
3
2JH,H = 13.4 Hz, 4 H, CHAHBAr), 3.9 (t, JH,H = 6.4 Hz, 8 H, CH O),
General procedure for preparation of 8–22
3.19 (d, J = 13.4 Hz, 4 H, CH HBAr), 1.90 (m, 8 H, CH CH22O),
2
To a solution of 5 (50 mg, 0.037 mmol) in CDCl3 (3 mL) was added
amines 5a–5o (0.148 mmol) and of 4Å molecular sieves (200 mg).
The solution was allowed to react without stirring at RT for 7–15 h.
After filtering, the CDCl3 was removed under reduced pressure.
Recrystallisation from chloroform/diethyl ether gave 8–10, 12–17, 21
and 22.
1.50–1.35 H(,mH , 8 H, OCH2CH2CHA), 1.23 (s, 36 H, C(CH3)3)21.00 (t,
3JH,H = 8.3 Hz, 12 H, CH CH ) p2pm. 13C NMR (100 MHz; CDCl3,
25 °C): δ = 164.8, 158.2, 31492.4, 143.2, 142.2, 126.6, 125.8, 125.5,
123.4 121.8, 121.4, 116.1, 72.4, 32.3, 31.4, 31.0, 19.3, 14.1; m/z (EI)
1458 [M+H]. Found C, 75.49; H, 7.61% C96H112O12 · 4H2O requires C,
75.36; H, 7.91%.
5,11,17,23-Tetrakis[(E)-2-(3-p-anisidineiminophenoxy)ethenyl]-
25,26,27,28-tetrabutoxycalix[4]arene (8): M.p. 102–107 °C; IR
5,11,17,23-Tetrakis[(E)-2-(4-methoxyphenoxycarbonyl)ethenyl]-
25,26,27,28-tetrabutoxycalix[4]arene (3): M.p. 160–162 °C. IR
(Nujol)/cm−1: 1732 (C=O), 1620 (C=C); 1H NMR (270 MHz; CDCl ,
1
(Nujol)/cm−1: 1720(C=O), 1635(C=N), 1589(C=C); H NMR (270
MHz; CDCl3, 25 °C): δ = 8.19 (s, 4 H, CH=N), 7.65–7.61 (m, 12 H,
25 °C): δ 7.58 (d, JH,H = 16.0 Hz, 4 H, Ar-CH=), 7.00 (d, JH,H = 9.30
Hz, 8 H, ArH), 6.85 (s, 8 H, ArH), 6.78 (d, 3JH,H = 9.0 Hz, 8 H, ArH),
6.28 (d, 3JH,H = 16.0 Hz, 4 H, Ar-CH=CH–C=O), 4.43 (d, 2JH,H = 13.4
Hz, 4 H, CHAHBAr), 3.93 (t, 3J = 6.4 Hz, 4 H, CH O), 3.76 (s, 12 H,
3
3
ArH + Ar-CH=), 7.31–7.30 (m, 4 H, ArH), 7.18–7.14 (m, 4 H, ArH),
3
7.13 (d, JH,H = 7.0 Hz, 8 H, ArH, (p-anisidine)), 6.94 (s, 8 H, ArH),
3
3
6.87 (d, JH,H = 7.0 Hz, 8 H, ArH (p-anisidine)), 6.36 (d, J = 16.1
Hz, 4 H, CH–C=O), 4.50 (d, 2JH,H = 13.6 Hz, 4 H, CHAHBArH),,H3.98 (t,
3J = 6.3 Hz, 8 H, OCH CH2), 3.77 (s, 12 H, OCH3), 3.26 (d,
2JHH,,HH = 13.6 Hz, CHAHBAr), 21.94–1.89 (m, 8 H, CH CH2O), 1.50–1.46
(m, 8 H, OCH2CH2CH2), 1.02 (t, 3JH,H = 8.4 Hz, 122H, CH3CH2) ppm.
13C NMR (1000 MHz; CDCl3, 25 °C): δ = 165.8, 159.4, 158.6, 157.4,
151.5, 146.9, 144.7, 138.0, 135.8, 129.7, 128.9, 126.6, 125.7, 122.5,
118.7, 117.2, 116.7, 115.3, 75.5, 55.9, 32.5, 31.7, 19.6, 14.0 ppm. m/z
(LSIMS) 1768 [M+ 4H]; Found C, 71.58; H, 5.96; N, 2.93%
CH3O), 3.19 (d, JH,H = 13.4 HH,Hz, 4 H, CHAHBAr2), 1.90 (m, 8 H,
3
CH2CH2O), 1.50–1.40 (m, 8 H, OCHCH2CH2 ), 1.00 (t, 3JH,H = 8.3 Hz,
12 H, CH3CH2) ppm. 13C NMR (100 MHz; CDCl3, 25 °C): δ = 165.4,
158.8, 156.81, 144.0, 135.1, 129.0, 128.1, 122.8, 122.6, 116.8, 116.4,
74.7, 55.3, 36.8, 32.1, 18.7, 14.1 ppm. m/z (EI) 1354 [M+H]. Found C,
72.65; H, 6.88% C84H O16 · 1.5H2O requires C, 73.08; H, 6.64%.
5,11,17,23-Tetrak8i8s[(E)-2-(phenoxycarbonyl)ethenyl]-25,26,
27,28-tetrabutoxycalix[4]arene (4): M.p. 92–94 °C. IR (Nujol)/cm−1:
1732 (C=O), 1634 (C=C); 1H NMR (270 MHz; CDCl , 25 °C):
C
112H108O16N4 · CHCl3 requires C, 71.98; H, 5.83; N, 2.97%.
5,11,17,23-Tetrakis[(E)-2-(3-anilineiminophenoxy)ethenyl]-25,26,
δ = 7.58 (d, JH,H = 16.0 Hz, 4 H, Ar-CH=), 7.28 (d, J =37.8 Hz, 8
H, ArH), 7.21 (t, 3JH,H = 7.8 Hz, 4 H, ArH), 7.11 (d, 3JHH,,HH = 7.8 Hz, 8
3
3
27,28-tetrabutoxycalix[4]arene (9): M.p. 91–94 °C. IR (Nujol)/cm−1:
1730 (C=O), 1640 (C=N), 1634 (C=C); 1H NMR (270 MHz; CDCl3,

66 JOURNAL OF CHEMICAL RESEARCH 2010
25 °C): δ = 8.16 (s, 4 H, CH=N), 7.60–7.15 (m, 12 H, Ar-CH=, ArH),
5,11,17,23-Tetrakis[(E)-2-(3-n-octyliminophenoxy)ethenyl]-25,
7.32–7.11 (m, 28 H, ArH + ArH(aniline)), 6.93 (s, 8 H, ArH), 6.28
26,27,28-tetrabutoxycalix[4]arene (15): M.p. 107–101 ºC. IR (Nujol)
3
2
1
/cm−1: 1732 (C=O), 1640 (C=N), 1634 (C=C); H NMR (270 MHz;
(d, JH,H = 14.9 Hz, 4 H, CH–C=O), 4.50 (d, JH,H = 12.8 Hz, 4 H,
3
CHAHBAr), 3.98–3.96 (m, JH,H = 8.3 Hz, 8 H, OCH2CH2), 3.27 (d,
CDCl3, 25 °C): δ = 8.06 (s, 4 H, CH=N), 7.61–7.56 (m, 8 H, ArH +
Ar-CH=), 7.44 (s, 4 H, ArH), 7.23–7.20 (m, 4 H, ArH), 7.15–7.13 (m,
4 H, ArH), 6.93 (s, 8 H, ArH), 6.32 (d, 3JH,H = 15.5 Hz, 4 H, CH–C=O),
4.50 (d, 2JH,H = 13.5 Hz, 4 H, CHAHBAr), 3.97 (t, 3JH,H = 6.7 Hz, 8 H,
OCH2CH2), 3.55 (t, 3JH,H = 6.7 Hz, 8 H, N–CH2), 3.25 (d, 3JH,H = 13.5
Hz, 4 H, CHAHBAr), 1.92–1.90 (m, 8 H, CH2CH2O), 1.65–1.62 (m, 8
H, NCH2CH2), 1.50–1.35 (m, 8 H, OCH2CH2CH2), 1.38–1.33 (m, 40
H, NCH2CH2(CH2)5CH3), 1.00 (t, 3JH,H = 8.3 Hz, 12 H, CH3CH2), 0.87
2JH,H = 12.8 Hz, 4 H, CHAHBAr), 1.98–1.91 (m, 8 H, CH2CH2O), 1.50–
1.35 (m, 8 H, OCH2CH2CH2), 1.00 (t, 3JH,H = 8.3 Hz, 12 H, CH3CH2)
ppm. 13C NMR (100 MHz; CDCl3, 25 °C): δ = 165.8, 159.6, 151.9,
159.4, 147.1, 137.8, 135.7, 129.6, 129.3, 126.2, 125.8, 125.1, 124.9,
122.6, 121.1, 121.1, 118.7, 115.3, 75.6, 31.5, 31.3, 19.5, 14.1 ppm.
m/z (LSIMS) 1646 [M+2H]; Found C, 73.80; H, 6.11; N, 3.1
C108H100O12N4 · CHCl3 requires C, 74.16; H, 5.77; N, 3.17
3
(t, JH,H = 6.2 Hz, 12 H, NCH2CH2(CH2)5CH3) ppm. 13C NMR (100
5,11,17,23-Tetrakis[(E)-2-(3-benzyliminophenoxy)ethenyl]-25,
26,27,28-tetrabutoxycalix[4]arene (10): M.p. 89–93 °C; IR (Nujol)
MHz; CDCl3, 25 °C): δ = 165.4, 161.1, 159.9, 157.3, 151.1, 146.6,
137.7 135.5, 129.6, 129.4, 128.7, 124.7, 124.0, 117.8, 75.2, 61.7, 32.2,
31.8, 30.9, 29.4, 29.3, 27.4, 26.7, 23.1, 22.6, 19.3, 14.1 ppm. m/z
(LSIMS) 1792 [M+2H]; Found C, 72.12; H, 8.32; N, 2.87% C116H148
O12N4 · 1.3CHCl3 requires C, 72.30; H, 7.72; N, 2.87%.
1
/cm−1: 1732 (C=O), 1640 (C=N), 1635 (C=C); H NMR (270 MHz;
CDCl3, 25 °C): δ = 8.17 (s, 4 H, CH=N), 7.61 (d, 3JH,H = 7.3 Hz, 4 H,
ArH), 7.60–7.15 (m, 36 H, Ar-CH=, ArH, ArH (benzylamine)), 6.92
(s, 8 H, ArH), 6.28 (d, 3JH,H = 15.2 Hz, 4 H, CH–C=O), 4.83 (s, 8 H,
CH2N=), 4.50 (d, 2JH,H = 12.8 Hz, 4 H, CHAHBAr), 3.97 (q, 3JH,H = 8.3
Hz, 8 H, OCH2CH2), 3.25 (d, 2JH,H = 12.8 Hz, 4 H, CHAHBAr), 1.92–
1.90 (m, 8 H, CH2CH2O), 1.50–1.35 (m, 8 H, OCH2CH2CH2), 1.00 (t,
3JH,H = 8.3 Hz, 12 H, CH3CH2) ppm. m/z (LSIMS) 1703 [M+2H];
Found C, 72.12; H, 6.13; N, 3.18% C112H108N4O12 · 1.5CHCl3 requires
C, 72.47; H, 5.87; N, 2.98%
5,11,17,23-Tetrakis[(E)-2-(3-(3-triethoxysilylpropyliminophenoxy)
)ethenyl]-25,26,27,28-tetrabutoxycalix[4]arene (16): M.p. 97–
1
101 °C. IR (Nujol)/cm−1: 1732 (C=O), 1640 (C=N), 1630 (C=C); H
NMR (270 MHz; CDCl3, 25 °C): δ = 8.01 (s, 4 H, CH=N), 7.49–7.48
(m, 8 H, ArH + Ar-CH=), 7.35 (s, 4 H, ArH), 7.20–7.18 (m, 4 H, ArH),
3
7.06 (d, JH,H = 7.7 Hz, 4 H, ArH), 6.85 (s, 8 H, ArH), 6.26 (d,
3JH,H = 15.5 Hz, 4 H, CH–C=O), 4.42 (d, 2JH,H = 13.4 Hz, 4 H, CHAH-
BAr), 3.90 (t, 3JH,H = 7.2 Hz, 8 H, OCH2CH2), 3.52 (t, 3JH,H = 7.2 Hz, 8
H, NCH2), 3.20 (d, 2JH,H =13.4 Hz, 4 H, CHAHBAr), 1.85–1.82 (m, 8 H,
CH2CH2O), 1.60–1.57 (m, 8 H, NCH2CH2), 1.42–1.37 (m, 8 H, OCH-
2CH2CH2), 1.31–1.13 (m, 60 H, Si–OCH2CH3 + OCH2CH3), 1.00 (t,
3JH,H = 8.4 Hz, 12 H, CH3CH2), 0.79 (m, 8 H, CH2Si) ppm. 13C NMR
(100 MHz; CDCl3, 25 °C): δ = 165.1, 159.7, 152.01, 146.4, 137.3,
135.1, 129.0, 128.2, 124.2, 123.5, 121.0 117.2, 115.6, 114.1, 74.7,
63.6, 57.7, 31.6, 29.1, 18.6, 17.6, 13.5, 7.3, 0.4 ppm. m/z (LSIMS)
2162 [M+5H] 2116 [M+4H-OCH2CH3]; Found C, 61.86; H, 6.87; N,
2.14 C120H164O24N4Si4 · 1.75CHCl3 requires C, 61.76; H, 7.06; N,
2.37%.
5,11,17,23-Tetrakis[(E)-2-(3-tryptiminophenoxy)ethenyl]-25,26,
27,28-tetrabutoxycalix[4]arene (12): M.p. 94–97 °C. IR (Nujol)/cm−1
1
1645 (C=N) 1680 (C=O), 1620(C=C); H NMR (270 MHz; CDCl3,
25 °C): δ = 7.90 (s, 4 H, CH=N), 7.83, (s, 4 H, ArH (tryptamine) 7.62–
7.58 (m, 16 H, ArH (tryptamine) + Ar-CH= + ArH), 7.34–7.32 (m, 8
H, ArH), 7.18–7.07 (m, 12 H, ArH (tryptamine)), 6.93 (s, 8 H, ArH),
6.31 (d, 3JH,H = 15.5 Hz, 4 H, CH–C=O) 4.50 (d, 2JH,H = 13.5 Hz, 4 H,
3
CHAHBAr), 3.97 (t, JH,H = 7.3 Hz, 8 H, OCH2CH2), 3.80 (m, 8 H,
CH2–N=), 3.26 (d, 2JH,H = 13.5 Hz, 4 H, CHAHBAr), 3.07 (t, 3JH,H = 6.23
Hz, 8 H, CH2CH2-Ar (tryptamine), 1.91–1.90 (m, 8 H, CH2CH2O),
3
1.50–1.35 (m, 8 H, OCH2CH2CH2), 1.00 (t, JH,H = 8.3 Hz, 12 H,
CH3CH2) ppm. 13C NMR (100MHz; CDCl3, 25 °C): δ = 165.5, 160.5,
159.8, 153.8, 151.2, 148.2, 146.7, 137.7, 136.2, 135.5, 129.4, 128.7,
124.9, 124.0, 122.5, 121.7, 121.6, 119.1, 118.8, 115.1, 113.6, 111.2,
75.3, 61.6, 32.2, 30.9, 26.5, 19.3, 14.0 ppm. m/z (LSIMS) 1917
[M+3H]; Found C, 69.32; H, 6.37; N, 5.06% C124H120O12N8 · 2.3
CHCl3 requires C, 69.19; H, 5.62; N, 5.11%.
5,11,17,23-Tetrakis[(E)-2-(3-(t-butyl-L-alanineiminophenoxy)ethe
nyl]-25,26,27,28-tetrabutoxycalix[4]arene (17): M.p. 89–94 °C. IR
(CH2Cl2)/cm−1: 1633 broad (C=N) and (C=C), 1710 broad (C=O) and
(C=O); 1H NMR (270 MHz; CDCl3, 25 °C): δ = 8.01 (s, 4 H, CH=N),
7.63–7.59 (m, 8 H, ArH + Ar-CH=), 7.49 (s, 4 H, ArH), 7.18–7.16 (m,
8 H, ArH), 6.90 (s, 8 H, ArH), 6.42 (d, 3JH,H = 15.4 Hz, 4 H, CH–C=O),
4.49 (d, 2JH,H = 13.4 Hz, 4 H, CHAHBAr), 3.97 (m, 12 H, OCH2CH2 +
CHCH3), 3.25 (d, 2JH,H = 13.4 Hz, 4 H, CHAHBAr), 1.95–1.91 (m, 8 H,
CH2CH2O), 1.55–1.39 (m, 56 H, OCH2CH2CH2 + (CH3)3C+ CHCH3),
5,11,17,23-Tetrakis[(E)-2-(3-allyliminophenoxy)ethenyl]-25,26,
27,28-tetrabutoxycalix[4]arene (13):M.p. 86–89 °C. IR (Nujol)/cm−1:
1
1732 (C=O), 1646 (C=C),1640 (C=N),1634 (C=C); H NMR (270
MHz; CDCl3, 25 °C): δ = 8.05 (s, 4 H, CH=N), 7.59 (m, 8 H, ArH,
Ar-CH=), 7.46 (s, 4 H, ArH), 7.35–7.18 (m, 8 H, ArH), 6.92 (s, 8 H,
3
1.00 (t, JH,H = 8.3 Hz, 12 H, CH3CH2) ppm. 13C NMR (100 MHz;
3
ArH), 6.30 (d, JH,H = 15.8 Hz, 4 H, CH–C=O), 6.10–5.90 (m, 4 H,
CDCl3, 25 °C): δ = 171.6, 165.5, 161.5, 159.2, 151.1, 146.7, 137.3,
136.8, 129.3, 128.6, 128.1, 125.2, 124.6, 122.1, 115.0, 81.1, 75.3,
68.4, 32.3, 31.0, 28.1, 28.0, 19.4, 14.0 ppm. m/z (LSIMS) 1856
[M+2H] 1728 [M+2H–(CH3)3COOCCH(CH3)N]; Found C, 66.99; H,
6.77; N, 2.50% C112H132O20N4 1.5CHCl3 requires C, 67.04%, H,
6.62%, N, 2.76.
3
CHCHD=CH ), 5.19 (d, JH,H = 15.0 Hz, 4 H, CHCHD=CH), 5.12 (d,
2
3JH,H = 10.9 Hz, 4 H, CHCHD=CH), 4.49 (d, JH,H = 13.7 Hz, 4 H,
CHAHBAr), 4.17 (d, 3JH,H = 4.9 Hz, 8 H, CH2-N=), 3.96 (t, 3JH,H = 7.0
Hz, 8 H, OCH2CH2), 3.25 (d, 2JH,H = 13.7 Hz, 4 H, CHAHBAr), 1.91–
1.89 (m, 8 H, CH2CH2O), 1.50–1.45 (m, 8 H, OCH2CH2CH2), 1.05 (t,
3JH,H = 8.3 Hz, 12 H, CH3CH2) ppm. 13C NMR (100 MHz; CDCl3,
25 °C): δ = 160.5, 150.6, 146.1, 139.2, 136.9, 136.1, 135.2, 134.8,
128.8, 128.1, 124.2, 123.6, 123.1, 121.4, 115.5, 114.4, 75.6, 44.0,
31.5, 31.3, 19.5, 14.1 ppm. m/z (LSIMS) 1502 [M+H]; Found C,
69.06, H, 6.89, 5.72% C96H100O12N4 · 1.5CHCl3 requires C, 69.67, H,
6.09%, N 3.33%.
5,11,17,23-Tetrakis[(E)-2-(3-furfuryliminophenoxy)ethenyl]-25,
26,27,28-tetrabutoxycalix[4]arene (21): M.p. 96–99 °C. IR (Nujol)
1
/cm−1: 1727 (C=O), 1632 (C=N), 1590 (C=C), H NMR (270 MHz;
CDCl3, 25 °C): δ = 8.12 (s, 4 H, CH=N), 7.63–7.55 (m, 8 H, ArH +
Ar-CH=), 7.47 (s, 4 H, ArH), 7.37–7.32 (m, 4 H, ArH(furfurylamine)),
7.26–7.25 (m, 4 H, ArH), 7.18–7.13 (m, 4 H,H ArH), 6.92 (s, 8 H,
ArH), 6.37–6.25 (m, 8 H, ArH(furfurylamine),+ CH–C=O), 6.25–6.20
(m, 4 H, ArH(furfurylamine)), 4.78–4.69 (m, 8 H, CH2N=), 4.50 (d,
2JH,H = 13.5 Hz, 4 H, CHAHBAr), 4.01–3.92 (m, 8 H, OCH2CH2), 3.25
5,11,17,23-Tetrakis[(E)-2-(3-n-butyliminophenoxy)ethenyl]-25,
26,27,28-tetrabutoxycalix[4]arene (14): M.p. 101–104 °C. IR (Nujol)
1
/cm−1: 1731 (C=O), 1633 (C=N), 1584 (C=C); H NMR (270 MHz;
CDCl3, 25 °C): δ = 8.06 (s, 4 H, CH=N), 7.61–7.55 (m, 8 H, ArH +
Ar-CH=), 7.46 (s, 4 H, ArH), 7.21–7.20 (m, 4 H, ArH), 7.14 (d,
3JH,H = 8.3 Hz, 4 H, ArH), 6.92 (s, 8 H, ArH), 6.33 (d, 3JH,H = 15.7 Hz,
2
(d, JH,H = 13.5 Hz, 4 H, CHAHBAr), 1.98–1.84 (m, 8 H, CH2CH2O),
1.56–1.35 (m, 8 H, OCH2CH2CH2), 1.01–0.97 (m, 12 H, CH3CH2)
ppm. 13C NMR (100 MHz; CDCl3, 25 °C): δ = 165.4, 162.1, 159.2,
152.2, 151.1, 146.7, 142.1, 137.2, 135.3, 130.5, 129.4, 128.6, 125.1,
124.5, 122.1, 115.0, 110.3, 107.5, 75.2, 57.1, 32.3, 31.0, 19.3, 14.0
ppm. m/z (LSIMS) 1663 [M+2H]; Found C, 67.84; H, 5.34; N, 3.16%
C104H100O16N4 1.75 CHCl3 requires C, 67.89; H, 5.48; N, 2.99%.
5,11,17,23-Tetrakis[(E)-2-(3-cyclohexyliminophenoxy)ethenyl]-
25,26,27,28-tetrabutoxycalix[4]arene (22): M.p. 97–101 °C. IR
2
4 H, CH–C=O), 4.50 (d, JH,H = 13.3 Hz, 4 H, CHAHBAr), 3.97 (t,
3JH,H = 6.8 Hz, 8 H, OCH2CH2), 3.53 (t, 3JH,H = 6.9 Hz, 8 H, N–CH2),
2
3.25 (d, JH,H = 13.3 Hz, 4 H, CHAHBAr), 1.92–1.90 (m, 8 H,
CH2CH2O), 1.67–1.62 (m, 8 H, NCH2CH2), 1.50–1.35 (m, 8 H,
OCH2CH2CH2), 1.38–1.33 (m, 8 H, NCH2CH2CH2), 1.00 (t, 3JH,H = 8.3
Hz, 12 H, CH3CH2), 0.91 (t, 3JH,H = 6.2 Hz, 12H, NCH2CH2CH2CH3)
ppm. 13C NMR (100 MHz; CDCl3, 25 °C): δ = 165.5, 159.9, 159.7,
151.2, 146.3, 137.7, 135.4, 129.4, 128.6, 124.7, 124.0, 121.8, 120.2,
116.3, 75.3, 61.3, 32.9, 32.2, 31.2, 20.4, 19.3, 14.1, 13.8 ppm. m/z
(LSIMS) 1564 [M+]; Found C, 71.74; H, 7.24; N, 2.96%
C100H116O12N4 · CHCl3 requires C, 71.98; H, 7.00; N 3.32%.
1
(Nujol)/cm−1: 1732 (C=O), 1640 (C=N), 1634 (C=C); H NMR (270
3
MHz; CDCl3, 25 °C): δ = 8.02 (s, 4 H, CH=N), 7.52 (d, JH,H = 15.4
3
Hz, 4 H, Ar-CH=), 7.49 (d, JH,H = 7.7 Hz, 4 H, ArH), 7.38 (s, 4 H,
ArH), 7.21–7.19 (m, 4 H, ArH), 7.12–7.11 (m, 4 H, ArH), 6.85 (s, 8 H,

JOURNAL OF CHEMICAL RESEARCH 2010 67
References
3
2
ArH), 6.25 (d, JH,H = 15.4 Hz, 4 H, CH–C=O), 4.42 (d, JH,H = 13.5
3
Hz, 4 H, CHAHBAr), 3.91 (t, JH,H = 7.2 Hz, 8 H, OCH CH2), 3.52–
1
2
3
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2
1.90–1.85 (m, 8 H, CH CH2O), 1.82–1.72 (m, 16 H, (CH) CHN),
1.61–1.59 (16H, m, (C2H2)2CH2), 1.27–1.24 (8H, m, (CH 2)2CH2),
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3
4
5
CH3CH2) ppm. 13C NMR (270 MHz; CDCl3, 25 °C): δ = 164.5, 158.1,
156.7, 150.1, 145.6, 137.0, 134.4, 128.3, 127.6, 124.5, 123.9, 122.9,
120.7, 114.1 74.3, 68.8, 33.3, 31.2, 30.0, 24.6, 23.7, 18.3, 14.3 ppm.
m/z (LSIMS) 1671 [M+2H]; Found C, 68.70; H, 7.36; N, 3.16%
C108H124O12N4 · 2CHCl3 requires C, 69.21; H, 6.65; N, 2.94%.
6
7
8
9
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To a solution of 7.7mmol of 5 in CDCl (2.0mL) was added 30.1mmol
of each of the amines 5a, 5c, 5e and 5g3. After 64h at room temperature
in the absence of stirring, the distribution of imine products was
determined via LSIMS-MS (see general experimental for equipment
details).
To determine a shift in imine product distribution in the presence of
a guest the above equilibration was repeated and after 64h 7.7mmol
of either 23 or 24 was added and the system allowed to equilibrate for
a further 48h at room temperature in the absence of stirring. The
distribution of imine products was then determined via LSIMS-MS.
LSIMS-MS data are available in supporting information.
17 K. N. Koh, K. Araki, A. Ikeda, H. Otsuka and S. Shinkai, J. Am. Chem.
Soc., 1996, 118, 755.
The authors thank EPSRC for funding (studentship to ALG),
Mr J. Bloxsidge, Mr R. Chaundy and Ms J. Peters for excellent
technical assistance. Practical work was carried out in the
Division of Chemistry, FHMS, University of Surrey, Guildford
GU2 7XH, UK.
18 N. Kuhnert and A. Le Gresley, J. Chem. Soc., Perkin Trans. 1, 2001, 3393.
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Ugozzoli and R. Ungaro, Eur. J. Org. Chem., 1998, 897.
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22 P. R. A. Webber, G. Z. Chen, M. G. B. Drew, P. D. Beer, Angew. Chem. Int.
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23 Y. Tokunaga, H. Sakon, H. Kanefusa, Y. Shimomura, K. Suzuki, Arkivoc,
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Received 6 November 2009; accepted 28 December 2009
Paper 090866 doi: 10.3184/030823410X12627159407690
Published online: 26 February 2010

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