Synthesis of polyfunctional phosphorus-containing calixarenes in cycloaddition reactions of azides to alkynes

Article abstract of DOI:10.1007/s10593-017-2005-0

Mono- and dibromo derivatives of calix[4]arene were used for the first time in phosphorylation, alkylation, and azide-alkyne cycloaddition sequence in order to synthesize polyfunctional macrocycles containing phosphine oxide groups at the upper rim and 1,

Full text of DOI:10.1007/s10593-017-2005-0

DOI 10.1007/s10593-017-2005-0
Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
Synthesis of polyfunctional phosphorus-containing calixarenes
in cycloaddition reactions of azides to alkynes
Nikita A. Drigo1, Alexander N. Gorbunov1, Dmitry N. Gorbunov1, Marta Yu. Talanova1,
Yulia S. Kardasheva1, Vladimir V. Kovalev1, Anton L. Maximov1, Ivan M. Vatsouro1*
1 M. V. Lomonosov Moscow State University,
1-3 Leninskie Gory , Moscow 119991, Russia; е-mail: vatsouro@petrol.chem.msu.ru
Submitted July 26, 2016
Accepted September 1, 2016
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
2016, 52(12), 1042–1053
X
P(=O)
X
Br
O
N
O
N
O
O
HO
OH
HO
OH
X = H, Br
N
N
N
N N
N N
N
N N
R
R
R
R
X = H, Ph2P, Ph2P=O
Mono- and dibromo derivatives of calix[4]arene were used for the first time in phosphorylation, alkylation, and azide-alkyne
cycloaddition sequence in order to synthesize polyfunctional macrocycles containing phosphine oxide groups at the upper rim and 1,4-di-
substituted triazole rings at the lower rim. The effect of reaction conditions onto the selectivity of the lower-rim alkylation of phosphorus-
containing calixarenes and the ratio of spatial isomers in the exaustively alkylated products was studied. The reduction of phosphine
oxide groups and modification of functional groups in the triazole rings were used for the synthesis of bulky hydrophilic phosphine-
containing ligands. The catalytic activity of in situ obtained rhodium complexes of phosphine-containing calixarenes was preliminarily
studied by 1-octene hydroformylation in ethanol.
Keywords: calixarenes, triazoles, click chemistry, hydroformylation, phosphines.
The rapid progress in the chemistry of calixarenes and
related compounds over the past 30 years has led to the
development of effective procedures for the functionali-
zation of these macrocycles by selective and exhaustive
modifications of the phenol hydroxy groups (the lower rim)
and/or activated para positions of the phenolic moieties
(the upper rim).1 Thereby, calixarenes can now be
considered as convenient scaffolds enabling the
combination and spatial pre-organization of various functi-
onal groups and recognition units in one molecule, and,
accordingly, for the design and synthesis of effective and
selective receptor molecules.
their analogs containing alkyl groups at the lower rim have
been found to be active catalysts of ethene or propene
oligomerization reactions3 and cross-coupling reactions (in
various modifications).4 Rhodium complexes of such
calixarenes are effective in catalytic hydrogenation of
linear and cyclic alkenes,5 as well as in alkene
hydroformylation reactions.6 At the same time, the
development of methods which allow the introduction of
functional groups not directly participating in the formation
of catalytically active complexes to the lower rim of
compounds 1 and 2 would give an opportunity for the
tuning of physicochemical characteristics of the catalysts
and, in particular, for immobilization of the catalysts on
extended surfaces.
Among the known calixarene derivatives, compounds
containing phosphine substituents at the upper rim have a
great potential for practical applications.2 Thus, for
example, nickel complexes of calixarenes 1, 2 (Fig. 1) and
The efficient building-block approach toward the syn-
thesis of polyfunctional organic molecules is the Cu(I)-ca-
0009-3122/16/52(12)-1042©2016 Springer Science+Business Media New York
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
Direct modification of the lower rim in compounds 1 and 2
by alkylation reactions seems possible only with simulta-
neous quaternization of phosphine groups, leading to a loss
of coordinating ability of P(III) atoms. Still, the synthesis
of acetylene-containing phosphines on the basis of
compounds 1 and 2 is theoretically possible by an
alternative chain of transformations, but the introduction of
such phosphines in CuAAC reaction would invariably lead
to their oxidation to P(V) derivatives upon interaction with
azides (the Staudinger reaction). For this reason, in this
work we studied a different approach, including the
transformations of calix[4]arenes containing a P=O group
in alkylation and CuAAC reactions, followed by reduction
of phosphine oxides to phosphines at the final steps of the
synthesis.
P
P
OH
HO
HO
OH
1
P
OH
HO
HO
OH
Ni2+-catalyzed Arbuzov reaction was used for
introducing phosphorus-containing substituents at the
upper rim of calixarenes.11 The available bromides 312 and
413 were reacted with O-isopropyl diphenyl phosphinite in
the presence of anhydrous NiCl2, while heating in diphenyl
ether. As a result, the phosphine oxides 5 and 6 were
obtained in high yields (Scheme 1). Compound 6 was
obtained for the first time, while the previously published
procedure for the synthesis of calixarene 5 relied on a
significantly larger number of steps.5
2
Figure 1. Phosphorus-containing calixarenes 1 and 2.
talyzed cycloaddition of azides to terminal alkynes
(CuAAC), leading to the formation of 1,4-disubstituted
triazoles. The data published so far indicate that the
CuAAC reaction has features required by a universal
method for the modification of polyfunctional molecules:
high selectivity, tolerance to many functional groups and
solvents of various nature.7 CuAAC reactions have been
used for the lower-rim modifications of calixarenes.8 For
example, we recently demonstrated that polyfunctional azides
can be used for obtaining heteroditopic receptors based on
calixarenes .9 Besides that, it was found that the addition of
first azide molecule to calixarenes containing between two,
three, or four acetylene groups at the lower rim can initiate a
cascade of sequential CuAAC reactions involving all
propargyl groups available for the azide addition.10
In the current work, we studied the possibility of using
CuAAC reactions as the key and universal step for the
modification of phosphorus-containing calixarenes. A
specific task of this study was also the creation of bulky
ligands with good solubility in polar media, which could be
used for rhodium-catalyzed hydroformylation of alkenes on
membrane-separable catalysts.
No literature references were found on the chemical
modification of free hydroxy groups at the lower rim of
calix[4]arenes containing diphenylphosphine oxide
substituents at the upper rim. For this reason, in this work
we performed optimization of reaction conditions for
exhaustive alkylation of calixarenes 5 and 6 at the lower
rim. The phosphine oxides 5 and 6 were used in reactions
with an excess of ethyl 2-bromoacetate in the presence of
Na2CO3, while refluxing in acetonitrile. As a result, the
ester derivatives 7 and 8 fixed in the cone conformation
were obtained for the first time (Scheme 2).
Exhaustive alkylation of compound 5 with the less
reactive propargyl bromide could not be accomplished
under the same conditions: mainly the starting calixarene
was recovered from the reaction mixture, containing a
Scheme 1
Br
Br
O
P
O
Ph2POi-Pr, NiCl2
P
Ph2O, 160°C, 5 h
HO
93%
OH
HO
OH
HO
OH
3
HO
OH
5
Br
O
Ph2POi-Pr, NiCl2
Ph2O, 160°C, 5 h
95%
P
HO
OH
HO
OH
HO
4
OH
HO
OH
6
1043

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
Scheme 2
O
P
O
P
O
O
O
P
P
Br
OEt
Na2CO3
MeCN, , 30 h
47%
OH
HO
5
HO
O
O
O
O
O
CH
O
EtO
O
OEt
O
OEt
9
OEt
O
7
O
P
O
P
O
O
P
Br
OEt
6
OH
HO
Na2CO3
MeCN, , 30 h
71%
OH
HC
O
O
O
O
O
EtO
10
O
O
OEt
O
O
OEt
OEt
Figure 2. Monopropargyl ethers 9 and 10, formed by reactions of
calixarene 5 and propargyl bromide in the presence of potassium
carbonate.
8
Scheme 3
small amount of the monoalkylated products. When
sodium carbonate was replaced with a stronger base,
potassium carbonate, a complex mixture of products was
obtained that did not contain the starting calixarene and
1
gave H NMR spectrum that allowed to identify only the
O
P
O
P
isomeric monopropargyl ethers 9 and 10 (Fig. 2). The
heating of calixarene 5 in a mixture with propargyl bromide
and cesium carbonate in DMF led to the formation of a
complex mixture of compounds, which was analyzed using
1Н NMR spectrum, but even the completeness of alkylation
at the lower rim of calixarene could not be determined.
The Mitsunobu reaction, commonly used for the
synthesis of calix[4]arenes distally disubstituted at the
lower rim,14 was also tested to get the dipropargyl ethers of
compound 5. However, despite the presence of bulky
substituents both in the starting calixarene and in the
reagent, the reaction of compound 5 with propargyl
alcohol, triphenylphosphine, and diisopropylazodicarboxy-
late (DIAD) proceeded non-selectively, giving a mixture of
OH
HO
O
O
CH
CH
11
HO
CH
Ph3P, DIAD
THF, rt, 24 h
+
5
O
P
O
P
1
isomeric ethers 11 and 12 according to H NMR data,
which could not be isolated and characterized as individual
samples (Scheme 3).
O
HO
OH
HC
O
The complex mixture of compounds, including the
tetrapropargyl ethers 13 and 14 fixed in cone and partial
cone conformations, respectively, was obtained by
alkylation of calixarene 5 with propargyl bromide in a
DMSO–H2O mixture, using NaOH as a base. Switching to
another strong base, NaH, and performing the synthesis in
THF with added DMF (5%)15 allowed to obtain the target
ether 13 as the main calixarene product of the reaction,
albeit with a very low conversion of the starting material 5.
The use of neat DMF without adding other solvents
allowed to achieve complete alkylation of the lower rim of
CH
12
calixarene 5 and to isolate a mixture of calixarenes 13 and
14 in 4:1 molar ratio and 68% overall yield. This mixture
could not be separated either by crystallization from
various solvents or by using column chromatography
(Scheme 4). The ratio of compounds 13 and 14 in the
mixture did not change after prolonged refluxing of its
1044

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
non-equivalent propargyl groups, as well as a single 31P
Scheme 4
1
NMR signal at 29.3 ppm. A set of less intense H NMR
signals could correspond to the structures of two different
tetraethers fixed in a partial cone conformation. However,
there was not one, but rather two 31P NMR signals of the
minor isomer at 29.4 and 28.4 ppm, allowing to
unequivocally assign them to the structure of compound 14
with alternating positions of two bulky substituents at the
upper rim.
O
O
P
P
O
O
O
O
It is likely that the steric repulsion between substituents
in calixarene 5 had the key role in facilitating the formation
of the isomer with partial cone conformation as the minor
product during the synthesis of compound 13 (in the case
of the ester derivative 7, the additional stabilization of the
isomer with cone conformation can be explained by the
interaction of Na+ ions with ester groups). This hypothesis
was confirmed by the results obtained during exhaustive
propargylation of calixarene 6, which contained only a
single phosphine oxide substituent at the upper rim: the
reaction of compound 6 with propargyl bromide in DMF in
the presence of sodium hydride gave only the ether 15,
fixed in the cone conformation, while no formation of other
isomers was detected (Scheme 5).
HC
CH
CH
CH
Br
13
CH
NaH
+
5
DMF, rt, 48 h
68%
CH
O
P
O
O
O
O
O
P
HC
HC
HC
Scheme 5
14
O
P
Br
CH
solution in toluene or during heating of a CDCl3 solution
while acquiring 1H NMR spectrum, pointing to the
conformational stability of the propargyl ethers. NMR
spectra of a mixture of compounds 13 and 14 are given in
Figure 3.
NaH
6
DMF, rt, 48 h
O
O
O
77%
O
HC
CH
15
CH
The structure of calixarene 13 fixed in the cone
conformation was evidenced, for example, by the presence
CH
1
of a pair of H NMR doublets due to ArCH2Ar protons at
4.59 and 3.19 ppm, two doublets (5.03 and 4.51 ppm), and
two triplets (2.49 and 2.44 ppm) of the protons from two
The propargylated calixarenes 13–15 were reacted with
azides in the presence of CuI·P(OEt)3 by heating in toluene.
In a reaction with ethyl 2-azidoacetate, the calixarene 15
was converted into compound 17 containing four ester
groups in triazole substituents (Scheme 6). When a mixture
of isomers 13 and 14 was used in a similar reaction, the
expected mixture of triazole-containing calixarenes (cone
and partial cone isomers) was obtained, from which the
individual compound 16 was successfully isolated by
column chromatography.
The polyfunctional azide 21 containing an
O-benzoylated tris(hydroxymethyl)aminomethane fragment
in its structure was also used as a component of CuAAC
reactions. The synthesis of compound 21 was achieved by
benzoylation of the N-protected tris(hydroxymethyl)-
aminomethane 18,16 followed by removal of the protecting
group from compound 19 and N-acylation of the amine 20
with azidoacetic acid that was activated with
diisopropylcarbodiimide (DIC) (Scheme 7).
Despite the significantly stronger steric hindrance in the
azide 21 compared to ethyl 2-azidoacetate, CuAAC
reactions with the participation of this compound were
successfully used for the synthesis of triazole-containing
1
Figure 3. 31P NMR (162 MHz) and H NMR spectra (400 MHz)
of a mixture of exhaustively propargylated calixarenes 13 and 14,
acquired in CDCl3 at 25°C.
1045

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
Scheme 6
Scheme 8
O
O
N
P
P
O
P
O
N
P
O
N
O
N
O
N
O
CuI.P(OEt)3
N3CH2CO2Et
CuI.P(OEt)3
13 (+ 14) + 21
O
N
PhMe, , 7 h
O
N
N
O
13 (+ 14)
O
N
N
N
N
52%
N
N
PhMe, , 7 h
N
N
42%
O
O
O
N
HN
N
N N
N N
N N
HN
O
NH
OBz
OBz
NH
O
EtO
OBz
BzO
O
EtO
O
BzO
BzO
OBz
OBz
O
OBz
OEt
OBz
BzO
OEt
BzO
16
22
O
P
O
P
N3CH2CO2Et
CuI.P(OEt)3
O
N
O
O
O
15
O
N
O
PhMe, , 7 h
O
N
O
CuI.P(OEt)3
N
N
N N
40%
15 + 21
N
O
N
N N
N N
N
N
N
N
PhMe, , 7 h
N
N
N
N
N
N
51%
O
N
EtO
O
EtO
O
OEt
O
O
O
HN
OEt
HN
O
NH
OBz
OBz
17
NH
OBz
BzO
BzO
BzO
OBz
OBz
OBz
Scheme 7
OBz
BzO
BzO
1) CF3CO2H,
CH2Cl2, rt, 12 h
NHBoc
NHBoc
23
BzCl, Et3N
compounds. In particular, in 1H NMR spectrum of
compound 22, the methylene bridges of the calixarene
scaffold gave two broadened doublets, while 1H NMR
spectrum of compound 23 contained two pairs of doublets,
pointing to syn orientation of all four aromatic rings of the
calixarene macrocycle (cone isomers) in both cases.
13C NMR spectra of compounds 22 and 23 provided little
information – the majority of signals in these spectra were
significantly broadened and/or substantially overlapped,
that was likely caused by the slow conformational
oscillations of the bulky substituents. The phosphine oxide
groups gave 31P NMR signals at 29.6 and 28.7 ppm in the
case of compounds 22 and 23, respectively. The mass
spectral data also confirmed the structures of these
compounds.
CH2Cl2
rt, 12 h
79%
2) Na2CO3, H2O
93%
OH
OBz
HO
HO
BzO
BzO
19
18
N3
NH2
N3CH2CO2H, DIC
CH2Cl2, rt, 12 h
90%
O
HN
OBz
BzO
BzO
20
OBz
BzO
BzO
21
calixarenes 22 and 23 (Scheme 8). Thus, the reaction of
calixarene 15 and azide 21 was used to obtain compound
23, fixed in the cone conformation and containing one
diphenylphosphine oxide substituent at the upper rim, as
well as four triazole substituents containing bulky groups at
the lower rim. The mixture of isomeric triazole-containing
calixarenes, formed in the reaction of propargyl ethers 13
and 14, was successfully separated by using column
chromatography, allowing to obtain of the calixarene 22 in
a good yield .
To get the phosphines capable of forming rhodium
complexes, the calixarene phosphine oxides 16, 17, 22, and
23 were reduced by phenylsilane upon prolonged refluxing
under inert atmosphere (Scheme 9). The reaction mixtures
1
after workup showed H NMR signals corresponding to
calixarene macrocycles, as well as triazole, ether, ester, and
amide functional groups. The phosphorus atoms gave
31P NMR signals between –5 and –7 ppm and the
impurities gave minor signals (~10%) between
The signals in 1Н NMR spectra of calixarenes 22 and 23
were broadened, but their positions and intensities
corresponded to the proposed structures of these
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
ing to the oxidized forms. 31P NMR spectra contained
characteristic phosphine signals at –6.6 and –4.8 ppm (for
compounds 24 and 25, respectively) along with the signals
of the oxidized forms at ~30 ppm, but the content of the
oxidized forms did not exceed 20%.
+28 and +30 ppm, indicating nearly complete reduction of
phosphine oxide groups to the respective phosphines.
The obtained crude phosphines were subjected to
hydrolysis reactions. According to the developed synthetic
strategy, the ester hydrolysis reactions were expected to
produce calixarenes containing one or two diphenyl-
phosphine moieties at the upper rim and polar carboxy or
hydroxymethyl groups as part of the substituents at the
lower rim. The treatment of calixarenes 16 and 17 with
potassium hydroxide in aqueous alcohol solution, followed
by acidification allowed to successfully synthesize the
tetracarboxylic acids 24 and 25 (Scheme 9). It was
unexpectedly observed that even in the absence of heating
the calixarenes 22 and 23 were hydrolyzed not only at the
ester groups, but also at the amide bonds, therefore the acids
24 and 25 were obtained also in this case. Model reactions
using non-reduced calixarenes 22 and 23 confirmed the low
stability of the amide bond toward alkaline hydrolysis. Thus,
the search of conditions suitable for selective removal of
benzoyl protecting groups from O-benzoylated tris-
(hydroxymethyl)methylamides required further experiments.
The possibility of using compounds 24 and 25 as
ligands for alkene hydroformylation catalyzed by rhodium
salts in ethanol medium was evaluated by performing
hydroformylation of 1-octene as a model substrate. The
rhodium complex [Rh(cod)2]BF4 (cod = 1,5-cyclooctadiene)
was used as rhodium source. In the course of these experi-
ments, it was found that ethanol or methanol solutions of
mixtures containing calixarene ligands and [Rh(cod)2]BF4
became cloudy after maintaining for 15–30 min at room
1
temperature. H NMR spectra of the solutions of such
mixtures in CD3OD (at the molar ratio of phosphine/Rh =
1:1), acquired within several minutes after preparation,
featured broadened and shifted proton signals, which were
assigned to compounds 24 and 25 (the characteristics of
signals assigned to the oxidized forms of compounds 24
1
and 25 did not change). Н NMR spectra of the same
samples, after maintaining for 2 h at room temperature and
already containing apparent amounts of precipitate,
featured signals that were assigned only to the oxidized
forms of calixarenes 24 and 25 (along with the signals of
1,5-cyclooctadiene released during the formation of
complexes). The obtained results allowed to propose that
the reactions of compounds 24 and 25 with [Rh(cod)2]BF4
generated predominantly oligomeric/polymeric complexes
that were insoluble in alcohols.
Scheme 9
P
P
i
i
O
N
16
22
O
N
O
N
O
The addition of D2SO4 to solutions containing mixtures
of ligands and [Rh(cod)2]BF4 (up to 1 % of D2SO4 in
CD3OD by volume) enabled to effectively suppress the
formation of insoluble reaction products – the solutions
remained homogeneous for at least 24 h. The signals of
~70%
~73%
N
N
N
N
N
N
N
N
N
O
O
HO
O
1
HO
O
OH
phosphines 24 and 25 in H NMR spectra of samples
OH
obtained with added D2SO4 were broadened and shifted
downfield, indicating the formation of cationic complexes.
At the same time, 31P NMR spectra contained signals due
to the oxidized forms of ligands (at ~30 ppm) that did not
participate in the reaction, as well as characteristic,
extremely broadened signals at ~24 ppm, corresponding to
the phosphorus atoms bonded to Rh+ ions (in the case of
the complex derived from calixarene 25, containing only one
phosphine moiety at the upper rim, 31P NMR spectrum con-
tained a well-visible broadened doublet with JRhP ~143 Hz).
The obtained data indicate that the calixarenes 24 and 25 in
the presence of sulfuric acid were able to form alcohol-
soluble rhodium complexes that were either monomeric or
with a low degree of oligomerization. More accurate
structural characterization of complexes obtained from
calixarenes 24 and 25 with or without the presence of
sulfuric acid would require additional experiments.
24
P
i
i
O
O
N
17
O
23
O
~60%
~67%
N
N
N
N
N
N
N
N
N
N
N
O
O
HO
O
HO
O
OH
OH
25
i: 1) PhSiH3, PhH, , 48 h2KOH, H2O, THF, rt, 15 h; 3) HCl, H2O
Due to the observed properties of rhodium complexes
of calixarenes 24 and 25, the preliminary study of the
activity of these compounds in hydroformylation reactions of
1-octene were performed in the absence or in presence of
H2SO4 by in situ preparation of the rhodium complexes
directly in the autoclave. The reaction conditions used and
Calixarenes 24 and 25 were readily soluble in alcohols.
1H NMR spectra acquired for their solutions in CD3OD
contained sets of signals corresponding to the structures of
1
calixarenes 24 and 25 (data of H–1H COSY spectra were
used for assigning the signals), as well as signals correspond-
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
the obtained results of the experiments are presented in
the diphenylphosphine substituents, but rather from the four
carboxymethyltriazolylmethyl groups, introduced at the
lower rim. Since the diffusion coefficients of complexes
obtained from calixarenes 24 and 25 were significantly
lower than those for PEG-1000, and taking into account the
fact that the diffusion coefficients are inversely
proportional to the particle radii (in the approximation of
Stokes–Einstein equation), the hydrodynamic radii of
rhodium complexes of compounds 24 and 25 can be
considered to be similar and exceeding 1 nm.
The obtained preliminary data allow to consider
calixarenes 24 and 25 as promising ligands for performing
alkene hydroformylation reactions catalyzed by rhodium
complexes in alcohol media, and using catalyst separation
by nanofiltration through membranes capable of separating
particles with minimum diameter of 2 nm.
Thus, in the current work we have developed a method
for the preparation of calix[4]arenes containing phosphine/
phosphine oxide substituents at the upper rim and
additional functional groups at the lower rim. A copper(I)
salt-catalyzed cycloaddition reaction of azides to alkynes
was used as the key step for introducing functional
substituents at the lower rim. For the specific purpose of
creating ligands soluble in polar media for applications in
hydroformylation reactions, the first phosphine-containing
calixarenes modified at the lower rim with carboxy-
methyltriazolylmethane moieties were created. Preliminary
studies have demonstrated that the rhodium complexes
prepared from the obtained phosphines showed catalytic
activity in hydroformylation reactions. The estimated
hydrodynamic radii of complexes indicated possibilities for
using them in catalytic reactions with membrane separation
of catalysts.
Table 1. From the data shown, it is evident that the addition of
ligands 24 and 25 improved the conversion of 1-octene in all
cases and facilitated an increase in the amount of reaction
products having the normal structure. The addition of
sulfuric acid allowed to achieve 100% conversion of alkene
and to significantly lower the amount of hydrogenation
products. It is probable that during the formation of
oligomeric/polymeric complexes of compounds 24 and 25
in the absence of acid, the number of rhodium atoms
available for the interaction with alkene was quite low,
decreasing the rate of the desired hydroformylation
reactions and, therefore, favoring the occurrence of side
reactions, such as hydrogenation.
For the purpose of catalytic reactions with membrane
separation of catalysts, the ligands and their complexes
have to be not only sufficiently soluble in suitable solvents,
but also must have the effective particle size corresponding
to the separation characteristics of membranes used for the
filtration.
The hydrodynamic radii of rhodium complexes of
calixarenes 24 and 25 obtained in the presence of D2SO4
were evaluated from the self-diffusion coefficients, deter-
mined by using 2D DOSY NMR spectra acquired in CD3OD
at 30°C. The decimal logarithms of these values, expressed
in m2/s, were found to be –9.42 (D 3.8×10–6 cm2/s) and
–9.39 (D 4.1×10–6 cm2/s) for the rhodium complexes of com-
pounds 24 and 25, respectively. The self-diffusion coeffi-
cient of PEG-1000 was determined for comparison under
identical conditions (logD (m2/s) –9.24, D 5.7×10–6 cm2/s).
The hydrodynamic radius of PEG-1000 in methanol at 30°C,
previously measured by the method of viscosimetry, was
equal to 0.916–0.933 nm.20
The somewhat lower value of diffusion coefficient for
the rhodium complex of calixarene 24, compared to that of
the complex of calixarene 25, was obviously caused by the
presence of not one, but two bulky substituents at the upper
rim of the molecule of compound 24, thus increasing the
size of the molecule. Nevertheless, the similar diffusion
coefficients for the complexes of calixarenes 24 and 25
indicate that the most significant contribution to the
molecular size and hydrodynamic properties was not from
Experimental
1H, 13C, and 31P NMR spectra were acquired on a Bruker
Avance 400 instrument (400, 100, and 162 MHz,
respectively), the chemical shifts (δ) are reported relative to
TMS (for H and 13C nuclei) and 85% H3PO4 (for 31P
1
nuclei); the signals were assigned on the basis of H–1H
1
COSY and 13С APT NMR spectra. The 2D DOSY spectra
Table 1. Reaction conditions and results of 1-octene hydroformylation*
Composition of reaction product mixture, %
Octene
conversion, %
Ligand
Hydrogenation
n-/iso-
(aldehydes + acetals)
Isomerization products
Aldehydes
Acetals
products
–
74
84
5
5
15
15
6
73
33
72
49
92
7
1.5
2
28
16
23
6
24
24**
25
100
92
5
2
10
4
18
2
2.5
2
25**
100
* Reaction conditions: p(CO–H2, 1:1) 5 MPa, temperature 80°C, time 3 h, 2 µmol of [Rh(cod)2]BF4, 1.9 mmol of 1-octene, 4 µmol of ligand 24 or 25,
2.5 ml of EtOH.
** Added 2 µmol of H2SO4.
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Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
3
4
were acquired on a Bruker Avance 600 instrument (600 MHz),
using ledbpgp2s pulse sequence21 with stimulated spin
echo, sinusoidal shaped gradient pulses of magnetic field
and time delay compensating for the influence of longitu-
dinal eddy currents; the change of current in the gradient
coil was stepwise (64 steps) from 2 to 95% of the maxi-
mum value (10 А); the maximum value of magnetic field
gradient (at the current of 10 А) G 53.5 Gauss/cm, the
diffusion time delay was 40 ms, the gradient pulse length
was 2 ms, relaxation delay was 1 s; the obtained array of
diffusion data was processed using the Bruker XWinNMR 3.5
software suite. High-resolution mass spectra were recorded
on a Thermo Scientific LTQ Orbitrap instrument with
electrospray ionization. Melting points were determined on
a Stuart SMP3 apparatus and were not corrected. The
composition of product mixtures from catalytic reactions was
analyzed by gas-liquid chromatography on an HP G1530A
chromatograph with a flame ionization detector, capillary
column (30 m) with SE-30 phase, with the temperature
programmed from 60 to 230°С, carrier gas – helium.
Commercially available reagents were used without
additional purification. The solvents were purified and
dried according to standard procedures. Ethyl
2-azidoacetate,17 azidoacetic acid,18 O-isopropyl diphenyl
phosphinite,19 compound 18,16 and calixarenes 3,12 413 were
synthesized according to published procedures.
H Ar); 6.88 (2H, dd, J = 7.6, J = 1.5, H Ar); 6.79 (1H, t,
3J = 7.6, H Ar); 6.71 (2H, t, J = 7.6, H Ar); 4.24 (4H, br. s,
3
ArCH2Ar); 3.56 (4H, br. s, ArCH2Ar). 13C NMR spectrum
(CDCl3), δ, ppm (J, Hz): 152.6 (d, JPC = 3.0, C Ar); 149.0,
148.3 (C Ar); 133.2 (d, JPC = 10.8, CH Ar); 132.6 (d,
J
PC = 104.3, C Ph); 132.1 (d, JPC = 10.0, CH Ph); 131.8 (d,
JPC = 2.7, CH Ph); 129.2, 129.1, 128.9 (CH Ar); 128.6 (d,
JPC = 13.2, C Ar); 128.3 (d, JPC = 12.2, CH Ph); 128.1,
128.0, 127.5 (C Ar); 124.8 (d, JPC = 108.0, C Ar); 122.5,
122.1 (CH Ar); 31.6, 31.5 (ArCH2Ar). 31P NMR spectrum
(CDCl3), δ, ppm: 30.1 (P=O). Found, m/z: 625.2145 [M+H]+.
C40H34O5P. Calculated, m/z: 625.2139.
5,17-Bis(diphenylphosphoryl)-25,26,27,28-tetra(ethoxy-
carbonylmethoxy)calix[4]arene (7). A mixture of calix-
arene 5 (0.063 g, 0.076 mmol), freshly calcined Na2CO3
(0.057 g, 0.54 mmol), and anhydrous acetonitrile (2 ml)
was refluxed with stirring for 1 h, treated with ethyl
2-bromoacetate (0.080 ml, 0.693 mmol), then the reaction
mixture was refluxed with stirring for additional 30 h and
cooled. The precipitate was filtered off, washed with
dichloromethane, and the combined filtrate was evaporated
by heating under vacuum. The residue after evaporation of
the solvent was separated by chromatography (eluting with
a concentration gradient of CH2Cl2–EtOH). Yield 0.043 g
1
(47%), white crystals, mp 160–162°C (ethanol). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.75–7.64 (8H, m,
5,17-Bis(diphenylphosphoryl)-25,26,27,28-tetrahydroxy-
calix[4]arene (5).5 A mixture of calixarene 3 (1.46 g,
2.5 mmol), NiCl2 (0.065 g, 0.5 mmol), and diphenyl ether
(30 ml) was stirred for 10 min at 160°C. Then a solution of
O-isopropyl diphenyl phosphinite (1.46 g, 6.0 mmol) in
diphenyl ether (15 ml) was added and the reaction mixture
was stirred for 5 h at 160°C. The reaction mixture was then
cooled and diluted with CH2Cl2 (50 ml), treated by the
addition of 15% aqueous Na2S2O3 solution (25 ml), and
vigorously stirred for 2 h. The organic layer was separated
and the aqueous layer was washed with CH2Cl2. The
combined organic extracts were washed with 2 N HCl
solution and water, filtered through a paper filter and
concentrated at reduced pressure. Hexane was added to the
obtained solution, the precipitate that formed was filtered
off, dried, and separated by chromatography (eluting with a
concentration gradient of CH2Cl2–EtOH). Yield 1.92 g
H Ph); 7.59–7.36 (16H, m, H Ar, H Ph); 6.29 (2H, t,
3J = 7.6, H Ar); 6.09 (4H, d, J = 7.6, H Ar); 4.99 (4H, s,
3
2
CH2CO); 4.84 (4H, d, J = 13.7, ArCH2Ar); 4.42 (4H, s,
3
CH2CO); 4.20 (4H, q, J = 7.2, CH2CH3); 4.16 (4H, q,
3J = 7.2, CH2CH3); 3.20 (4H, d, 2J = 13.7, ArCH2Ar); 1.26
3
3
(6H, t, J = 7.2, CH2CH3); 1.25 (6H, t, J = 7.2, CH2CH3).
13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 170.3, 169.3
(C=O); 160.3 (d, JPC = 3.3, C Ar); 154.6 (C Ar); 136.9 (d,
JPC = 13.2, C Ar); 133.3 (d, JPC = 10.6, CH Ar); 132.9 (d,
JPC = 103.9, C Ph); 132.1 (d, JPC = 9.9, CH Ph); 132.0
(C Ar); 131.8 (d, JPC = 2.6, CH Ph); 128.4 (d, JPC = 12.1,
CH Ph); 128.1 (CH Ar); 126.1 (d, JPC = 106.8, C Ar); 123.2
(CH Ar); 71.7, 71.0 (CH2CO); 60.8, 60.5 (CH2CH3); 31.3
(ArCH2Ar); 14.2, 14.1 (CH3). 31P NMR spectrum (DMSO-d6),
δ, ppm: 25.6 (P=O). Found, m/z: 1191.3797 [M+Na]+.
C68H66NaO14P2. Calculated, m/z: 1191.3820.
5-Diphenylphosphoryl-25,26,27,28-tetra(ethoxycarbo-
nylmethoxy)calix[4]arene (8) was obtained analogously to
the procedure for preparation of compound 7 from
calixarene 6 (0.125 g, 0.20 mmol), freshly calcined Na2CO3
(0.148 g, 1.40 mmol), ethyl 2-bromoacetate (0.208 ml,
1.80 mmol), and anhydrous acetonitrile (5 ml). Yield 0.138 g
(71%), white crystals, mp 84–89°C (ethanol). 1H NMR
spectrum (CDCl3,), δ, ppm (J, Hz): 7.50–7.42 (2H, m,
H Ph); 7.41–7.28 (8H, m, H Ph); 6.88 (2H, d, JPH = 12.2,
1
(93%), white crystals, mp 258–260°C (EtOH). H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 10.15 (4H, br. s, OH);
7.67–7.59 (8H, m, H Ph); 7.56–7.50 (4H, m, H Ph); 7.47–
3
7.36 (12H, m, H Ar, H Ph); 6.86 (4H, d, J = 7.5, H Ar);
3
6.66 (2H, t, J = 7.5, H Ar); 4.21 (4H, br. s, ArCH2Ar);
3.52 (4H, br. s, ArCH2Ar).
5-Diphenylphosphoryl-25,26,27,28-tetrahydroxycalix-
[4]arene (6) was obtained analogously to the procedure for
obtaining compound 5, using calixarene 4 (1.67 g, 3.3 mmol),
NiCl2 (0.044 g, 0.33 mmol), O-isopropyl diphenyl phos-
phinite (0.98 g, 3.96 mmol), and diphenyl ether (54 ml).
Yield 1.96 g (95%), white crystals, mp 166–168°C (hexane).
1H NMR spectrum (CDCl3,), δ, ppm (J, Hz): 10.21 (4H, br. s,
OH); 7.67–7.59 (4H, m, H Ph); 7.55–7.48 (2H, m, H Ph);
7.46–7.39 (4H, m, H Ph); 7.39 (2H, d, JPH = 11.9, H Ar);
3
3
H Ar); 6.83 (2H, d, J = 6.8, H Ar); 6.71 (2H, d, J = 6.8,
3
3
H Ar); 6.61 (2H, d, J = 7.4, H Ar); 6.57 (2H, t, J = 6.8,
3
2
H Ar); 6.51 (1H, t, J = 7.4, H Ar); 4.91 (2H, d, J = 13.4,
2
ArCH2Ar); 4.88 (2H, d, J = 13.4, ArCH2Ar); 4.87 (2H, d,
2J = 16.3, OCH2); 4.80 (2H, d, 2J = 16.3, OCH2); 4.69 (2H,
3
s, OCH2); 4.67 (2H, s, OCH2); 4.22 (2H, q, J = 7.2,
3
CH2CH3); 4.20 (2H, q, J = 7.2, CH2CH3); 4.17 (4H, q,
7.11 (2H, d, 3J = 7.6, H Ar); 7.06 (2H, dd, 3J = 7.6, J = 1.5,
3J = 7.1, CH2CH3); 3.27 (2H, d, 2J = 13.4, ArCH2Ar); 3.18
4
1049

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
(2H, d, 2J = 13.4, ArCH2Ar); 1.29 (3H, t, 3J = 7.2,
(d, JPC = 3.1, C Ar); 155.0, 154.6, 136.3, 135.9 (C Ar);
135.0 (d, JPC = 13.2, C Ar); 134.5 (C Ar); 132.7 (d,
3
CH2CH3); 1.27 (3H, t, J = 7.2, CH2CH3); 1.26 (6H, t,
3J = 7.1, CH2CH3). 13C NMR spectrum (CDCl3), δ, ppm
(J, Hz): 170.1, 169.7, 169.4 (C=O); 158.7 (d, JPC = 3.3,
C Ar); 155.7, 155.5 (C Ar); 134.8 (C Ar); 134.7 (d,
JPC = 11.3, CH Ar); 132.5 (d, JPC = 103.5, C Ph); 131.7 (d,
PC = 9.7, CH Ph); 131.2 (d, JPC = 2.8, CH Ph); 128.6, 128.4
J
(CH Ar); 128.0 (d, JPC = 12.0, CH Ph); 127.8 (CH Ar); 125.8
(d, JPC = 106.7, C Ar); 123.8, 123.3 (CH Ar); 80.6, 79.9,
79.3 (CCH); 75.4, 75.0, 74.8 (CCH); 61.8 (2С), 60.6
(OCH2); 31.9, 31.7 (ArCH2Ar). 31P NMR spectrum
(CDCl3), δ, ppm: 28.5 (P=O). Found, m/z: 777.2768 [M+H]+.
C52H42O5P. Calculated, m/z: 777.2765.
JPC = 13.2, C Ar); 134.3, 134.2 (C Ar); 132.9 (d, JPC = 11.3,
CH Ar); 132.5 (d, JPC = 104.0, C Ph); 131.8 (d, JPC = 9.9,
CH Ph); 131.3 (d, JPC = 2.6, CH Ph); 128.8, 128.6, 128.3
(CH Ar); 128.1 (d, JPC = 12.1, CH Ph); 125.4 (d,
JPC = 107.6, C Ar); 123.3, 123.0 (CH Ar); 71.6, 71.3, 71.1
(CH2CO); 60.6, 60.5, 60.4 (CH2CH3); 31.4, 31.2
(ArCH2Ar); 14.1 (CH3). 31P NMR spectrum (CDCl3), δ, ppm:
28.8 (P=O). Found, m/z: 991.3433 [M+Na]+. C56H57NaO13P.
Calculated, m/z: 991.3430.
5,17-Bis(diphenylphosphoryl)-25,26,27,28-tetra-
(1-ethoxycarbonylmethyl-4-triazolylmethoxy)calix[4]arene
(16). A mixture of calixarenes 13 and 14 (0.39 g, 0.4 mmol),
ethyl 2-azidoacetate (0.26 g, 2.0 mmol), CuI·P(OEt)3 (0.02 g,
0.06 mmol), and anhydrous toluene (12 ml) was refluxed
with stirring for 7 h. The solvent was evaporated, the
residue was diluted with CH2Cl2, and the solution was
washed with 2 N HCl. The organic extracts were washed
with water, filtered through a paper filter and evaporated at
reduced pressure. The residue was separated by
chromatography (eluting with a concentration gradient of
CH2Cl2–EtOH). Yield 0.25 g (42%), white crystals, mp 124–
126°C (ethanol). 1H NMR spectrum (CDCl3), δ, ppm (J, Hz):
7.91 (2H, s, H triazole); 7.79 (2H, s, H triazole); 7.67–7.40
(20H, m, H Ph); 7.29 (4H, d, JPH = 12.0, H Ar); 6.28 (2H, t,
5,17-Bis(diphenylphosphoryl)-25,26,27,28-tetra(2-pro-
pynyloxy)calix[4]arene (13) (in a mixture with compound
14). A suspension of calixarene 5 (1.14 g, 1.38 mmol) in
anhydrous DMF (35 ml) was treated with sodium hydride
(60% suspension in mineral oil, 0.33 g). The mixture was
stirred under moisture-free atmosphere for 1 h. Propargyl
bromide (80% solution in toluene, 1.19 ml, 11.0 mmol)
was added with stirring. The reaction mixture was stirred in
a sealed flask at room temperature for 48 h. Water (80 ml)
was added with caution while stirring and the reaction
products were extracted with CH2Cl2 (5×30 ml). The
combined organic extracts were washed with water, filtered
through a paper filter, and evaporated at reduced pressure.
The residue was separated by chromatography (eluting
with a concentration gradient of CH2Cl2–EtOH). Yield (4:1
mixture of compounds 13/14) 0.92 g (68%), yellowish-
3
3J = 7.6, H Ar); 6.08 (4H, d, J = 7.6, H Ar); 5.21 (4H, s,
OCH2); 5.14 (4H, s, NCH2); 5.13 (4H, s, NCH2); 4.83 (4H,
2
s, OCH2); 4.24 (4H, d, J = 13.5, ArCH2Ar); 4.18 (4H, q,
3
3J = 7.1, CH2CH3); 4.13 (4H, q, J = 7.1, CH2CH3); 3.00
(4H, d, 2J = 13.5, ArCH2Ar); 1.23 (6H, t, 3J = 7.1,
1
3
brown solid. H NMR spectrum (CDCl3, signals reported
CH2CH3); 1.19 (6H, t, J = 7.1, CH2CH3). 13C NMR
only for compound 13), δ, ppm (J, Hz): 7.72–7.62 (8H, m,
spectrum (CDCl3), δ, ppm (J, Hz): 166.6, 166.2 (C=O);
159.0 (d, JPC = 2.9, C Ar); 154.2 (C Ar); 144.2, 143.9
(C triazole); 137.7 (d, JPC = 13.4, C Ar); 132.9 (d,
JPC = 11.5, CH Ar); 132.8 (d, JPC = 104.3, C Ph); 132.5
(C Ar); 132.1 (d, JPC = 9.9, CH Ph); 131.7 (d, JPC = 2.2,
CH Ph); 128.4 (d, JPC = 12.1, CH Ph); 127.9 (CH Ar);
126.1 (CH triazole); 125.9 (d, JPC = 107.0, C Ar); 125.4
(CH triazole); 123.0 (CH Ar); 67.8, 65.6 (OCH2); 62.2,
62.0 (CH2CH3); 50.8, 50.7 (NCH2); 31.1 (ArCH2Ar); 14.0,
13.9 (CH3). 31P NMR spectrum (CDCl3), δ, ppm: 29.8
(P=O). Found, m/z: 747.2683 [M+2H]2+. C80H80N12O14P2.
Calculated, m/z: 747.2691.
H Ph); 7.60–7.36 (16H, m, H Ar, H Ph); 6.38 (2H, t,
3
3J = 7.5, H Ar); 6.24 (4H, d, J = 7.5, H Ar); 5.03 (4H, d,
2
4J = 2.4, OCH2); 4.59 (4H, d, J = 13.5, ArCH2Ar); 4.51
(4H, d, 4J = 2.4, OCH2); 3.19 (4H, d, 2J = 13.5, ArCH2Ar);
4
4
2.49 (2H, t, J = 2.4, CCH); 2.44 (2H, t, J = 2.4, CCH).
31P NMR spectrum (CDCl3, only the signal of compound
13 reported), δ, ppm: 29.3 (P=O). Found, m/z: 977.3163
[M+H]+. C64H51O6P2. Calculated, m/z: 977.3156.
5-Diphenylphosphoryl-25,26,27,28-tetra(2-propynyloxy)-
calix[4]arene (15) was obtained analogously to the proce-
dure for preparation of compound 13, using calixarene 6
(1.32 g, 2.12 mmol), sodium hydride (60% suspension in
mineral oil, 0.51 g, 12.7 mmol), propargyl bromide (80%
solution in toluene, 1.83 ml, 17.0 mmol), and anhydrous
DMF (40 ml). Yield 1.26 g (77%), yellowish-brown
crystals, mp 117–119°C (ethanol). 1H NMR spectrum
(CDCl3), δ, ppm (J, Hz): 7.47–7.41 (2H, m, H Ph); 7.31–
7.20 (8H, m, H Ph); 7.02–6.97 (2H, m, H Ar); 6.78 (2H, d,
JPH = 12.3, H Ar); 6.73–6.70 (6H, m, H Ar); 6.68 (2H, d,
3J = 7.5, H Ar); 6.47 (1H, t, 3J = 7.5, H Ar); 4.96 (2H, dd,
2J = 16.2, 4J = 2.4, OCH2); 4.90 (2H, dd, 2J = 16.2, 4J = 2.4,
OCH2); 4.68 (2H, d, 4J = 2.4, OCH2); 4.67 (2H, d, 4J = 2.4,
5-Diphenylphosphoryl-25,26,27,28-tetra(1-ethoxy-
carbonylmethyl-4-triazolylmethoxy)calix[4]arene (17)
was obtained analogously to the procedure for preparation
of compound 16, using calixarene 15 (0.39 g, 0.5 mmol),
ethyl 2-azidoacetate (0.32 g, 2.5 mmol), CuI·P(OEt)3 (0.03 g,
0.08 mmol), and toluene (15 ml). Yield 0.26 g (40%),
white crystals, mp 110–112°C (ethanol). 1H NMR
spectrum (CDCl3), δ, ppm (J, Hz): 7.98 (1H, s, H triazole);
7.82 (1H, s, H triazole); 7.78 (2H, s, H triazole); 7.47–7.42
(2H, m, H Ph); 7.33–7.27 (8H, m, H Ph); 6.87–6.82 (2H,
m, H Ar); 6.78 (2H, d, JPH = 12.3, H Ar); 6.67 (2H, d,
3J = 7.5, H Ar); 6.59 (2H, t, 3J = 7.5, H Ar); 6.55–6.51 (2H,
2
OCH2); 4.64 (2H, d, J = 13.4, ArCH2Ar); 4.63 (2H, d,
2
3
2J = 13.4, ArCH2Ar); 3.27 (2H, d, J = 13.4, ArCH2Ar);
br. d, H Ar); 6.46 (1H, t, J = 7.5, H Ar); 5.17 (2H, s,
2
4
3.15 (2H, d, J = 13.4, ArCH2Ar); 2.50 (1H, t, J = 2.4,
NCH2); 5.15 (4H, s, NCH2); 5.14 (2H, s, NCH2); 5.10 (2H,
4
4
2
2
CCH); 2.47 (2H, t, J = 2.4, CCH); 2.46 (1H, t, J = 2.4,
CCH). 13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 157.6
d, J = 12.6, OCH2); 5.04 (2H, d, J = 12.6, OCH2); 5.01
(2H, s, OCH2); 5.00 (2H, s, OCH2); 4.34 (2H, d, 2J = 13.3,
1050

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
3
ArCH2Ar); 4.21 (2H, q, J = 7.1, CH2CH3); 4.20 (4H, q,
Tris(benzoyloxymethyl)methylamide of 2-azidoacetic
3J = 7.1, CH2CH3); 4.19 (2H, q, J = 7.1, CH2CH3); 4.18 acid (21). A mixture of amine 20 (6.00 g, 13.9 mmol),
3
2
2
(2H, d, J = 13.3, ArCH2Ar); 3.14 (2H, d, J = 13.3, 2-azidoacetic acid (1.60 g, 15.8 mmol), and anhydrous
2
ArCH2Ar); 2.93 (2H, d, J = 13.3, ArCH2Ar); 1.26 (9H, t, CH2Cl2 (80 ml) was treated with diisopropylcarbodiimide
3J = 7.1, CH2CH3); 1.25 (3H, t, 3J = 7.1, CH2CH3). (2.28 ml, 14.7 mmol). The reaction mixture was stirred at
13C NMR spectrum (CDCl3), δ, ppm (J, Hz): 166.6, 166.5, room temperature for 12 h. The obtained mixture was
166.4 (C=O); 158.0 (d, JPC = 2.6, C Ar); 155.0, 154.8 treated with 2 N HCl and vigorously stirred for 1 h. The
(C Ar); 144.5, 144.4, 143.9 (C triazole); 135.9, 135.3 organic layer was separated, and the aqueous layer was
(C Ar); 135.2 (d, JPC = 13.5, C Ar); 134.7 (C Ar); 132.9 (d, washed with CH2Cl2. The combined organic extracts were
J
PC = 11.5, CH Ar); 132.7 (d, JPC = 102.7, C Ph); 131.9 (d, washed with water, filtered through a paper filter, and
JPC = 9.5, CH Ph); 131.2 (d, JPC = 2.0, CH Ph); 128.7, evaporated. Yield 6.44 g (90%), white crystals, mp 119–
1
128.4 (CH Ar); 128.1 (d, JPC = 11.8, CH Ph); 128.1 121°C (dichloromethane). H NMR spectrum (CDCl3), δ,
(CH Ar); 125.9, 125.8 (2С) (CH triazole); 125.4 (d, ppm: 8.04–7.95 (6H, m, H Ph); 7.59–7.51 (3H, m, H Ph);
JPC = 108.1, C Ar); 123.3, 122.9 (CH Ar); 67.6, 67.3, 66.2 7.45–7.36 (6H, m, H Ph); 7.21 (1H, s, NH); 4.90 (6H, s,
(OCH2Trz); 62.2 (CH2CH3); 50.9, 50.8 (2С) (NCH2); 31.3, OCH2); 3.95 (2H, s, CH2N3). 13C NMR spectrum (CDCl3),
31.1 (ArCH2Ar); 14.1 (br. s, CH3). 31P NMR spectrum δ, ppm: 167.1, 166.1 (C=O); 133.5, 129.7 (CH Ph); 129.1
(CDCl3), δ, ppm: 28.9 (P=O). Found, m/z: 647.2490 (C Ar); 128.5 (CH Ar); 63.5 (OCH2); 59.2 (NC(CH2)3);
[M+2H]2+. C68H71N12O13P. Calculated, m/z: 647.2496.
tert-Butyl-N-[tris(benzoyloxymethyl)methyl]carba-
mate (19). A mixture of carbamate 18 (10.70 g,
53.0 (N3CH2). Found, m/z: 539.1556 [M+Na]+.
C27H24NaN4O7. Calculated, m/z: 539.1538).
5,17-Bis(diphenylphosphoryl)-25,26,27,28-tetra-
48.4 mmol), Et3N (23.3 ml, 167.4 mmol), and anhydrous [1-tris(benzoyloxymethyl)methylaminocarbonylmethyl-
CH2Cl2 (160 ml) was stirred and slowly treated by 4-triazolylmethoxy]calix[4]arene (22) was prepared analo
dropwise addition of a solution of benzoyl chloride -gously to the procedure for obtaining compound 16, by using
(18.3 ml, 157.7 mmol) in CH2Cl2 (40 ml). The reaction a mixture of calixarenes 13 and 14 (0.49 g, 0.5 mmol), azide
mixture was stirred for 12 h. The obtained mixture was 21 (1.29 g, 2.5 mmol), CuI·P(OEt)3 (0.03 g, 0.08 mmol),
quenched with water and portionwise addition of NaHCO3 and toluene (30 ml). Yield 0.79 g (52%), yellow crystals,
1
until the evolution of gas ceased. The organic layer was
mp 163–165°C (ethanol). H NMR spectrum (CDCl3),
separated, and the aqueous layer was washed with CH2Cl2. δ, ppm (J, Hz): 8.05 (2H, br. s, H triazole); 8.01–7.80 (26H,
The combined organic extracts were washed with water, m, H Ph, H triazole); 7.71–7.60 (10H, m, H Ph); 7.55–7.20
3
filtered through a paper filter, and evaporated. The residue (54H, m, H Ar, H Ph, NH); 6.27 (2H, t, J = 7.6, H Ar);
after evaporation of solvent was recrystallized from ethanol 6.05 (4H, d, 3J = 7.6, H Ar); 5.15 (4H, s, NCH2); 4.98 (4H,
and separated by chromatography (eluting with
a
s, NCH2); 4.90 (4H, s, OCH2); 4.81 (12H, s, CH2OBz);
concentration gradient of CH2Cl2–EtOH). Yield 20.4 g 4.80 (12H, s, CH2OBz); 4.65 (4H, s, OCH2); 4.25 (4H, br.
(79%), white crystals, mp 124–126°C (ethanol). H NMR d, 2J = 13.1, ArCH2Ar); 3.02 (4H, br. d, J = 13.1,
1
2
3
31
spectrum (CDCl3), δ, ppm (J, Hz): 8.01 (6H, d, J = 7.6, ArCH2Ar). P NMR spectrum (CDCl3), δ, ppm: 29.6 (P=O).
H Ph); 7.55 (3H, t, J = 7.6, H Ph); 7.40 (6H, t, J = 7.6, Found, m/z: 1521.4914 [M+2H]2+. C172H148N16O34P2.
3
3
H Ph); 5.25 (1H, s, NH); 4.82 (6H, s, OCH2); 1.41 (9H, s, Calculated, m/z: 1521.4904.
C(CH3)3). 13C NMR spectrum (CDCl3), δ, ppm (J, Hz):
5-Diphenylphosphoryl-25,26,27,28-tetra[1-tris(benzo-
166.0, 154.4 (C=O); 133.3, 129.7 (CH Ph); 129.4 (C Ph); yloxymethyl)methylaminocarbonylmethyl-4-triazolyl-
128.4 (CH Ph); 80.2 (OC(CH3)3) 64.0 (OCH2); 57.5 (NC methoxy]calix[4]arene (23) was prepared analogously to
(CH2)3); 28.2 (C(CH3)3). Found, m/z: 534.2098 [M+H]+. the procedure for obtaining compound 16, using calixarene
C30H32NO8. Calculated, m/z: 534.2122.
15 (0.55 g, 0.7 mmol), azide 21 (1.81 g, 3.5 mmol), CuI·P
Tris(benzoyloxymethyl)methylamine (20). A solution of (OEt)3 (0.04 g, 0.11 mmol), and toluene (35 ml). Yield 1.02
1
carbamate 19 (8.00 g, 15.0 mmol) in CH2Cl2 (120 ml) was g (51%), yellow crystals, mp 153–155°C (ethanol). H
treated by the addition of CF3CO2H (11.5 ml, 150.0 mmol). NMR spectrum (CDCl3), δ, ppm (J, Hz): 7.98–7.82 (28H,
The reaction mixture was stirred at room temperature for m, H triazole, H Ph); 7.67 (2H, s, H triazole); 7.49–7.33
12 h. The mixture was poured into 0.1 М aqueous solution (20H, m, H Ph); 7.32–7.19 (28H, m, H Ph, NH); 6.81 (2H,
of Na2CO3 and stirred until complete dissolution of the d, 3J = 7.6, H Ar); 6.67 (2H, d, JPH = 12.0, H Ar); 6.55 (2H,
precipitate. The organic layer was separated and the d, 3J = 7.6, H Ar); 6.54 (2H, t, 3J = 7.6, H Ar); 6.43 (2H, d,
3
aqueous layer was washed with CH2Cl2. The combined 3J = 7.1, H Ar); 6.35 (1H, t, J = 7.1, H Ar); 5.08 (2H, s,
organic extracts were washed with water, filtered through NCH2); 5.07 (2H, s, NCH2); 5.01 (4H, s, NCH2); 4.91 (4H,
paper filter, and evaporated. Yield 6.04 g (93%), white s, OCH2Trz); 4.84 (4H, s, OCH2Trz); 4.83 (24H, s,
2
crystals, mp 107–109°C (dichloromethane). 1H NMR CH2OBz); 4.26 (2H, d, J = 13.2, ArCH2Ar); 4.15 (2H, d,
3
2
spectrum (CDCl3), δ, ppm (J, Hz): 8.03 (6H, d, J = 7.6, 2J = 13.2, ArCH2Ar); 3.03 (2H, d, J = 13.3, ArCH2Ar);
3
3
2
H Ph); 7.55 (3H, t, J = 7.6, H Ph); 7.41 (6H, t, J = 7.6, 2.82 (2H, d, J = 13.3, ArCH2Ar). 31P NMR spectrum
H Ph); 4.52 (6H, s, OCH2). 13C NMR spectrum (CDCl3), δ, (CDCl3), δ, ppm: 28.7 (P=O). Found, m/z: 1421.4705
ppm: 166.0 (C=O); 133.3, 129.6 (CH Ph); 129.4 (C Ph); 128.5 [M+2H]2+. C160H139N16O33P. Calculated, m/z: 1421.4709.
(CH Ph); 66.4 (OCH2); 54.9 (CNH2). Found, m/z: 434.1602
5,17-Bis(diphenylphosphanyl)-25,26,27,28-tetra-
(1-carboxymethyl-4-triazolylmethoxy)calix[4]arene
[M+H]+. C25H24NO6. Calculated, m/z: 434.1598.
1051

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
(24). A suspension of calixarene 16 or calixarene 22
80°С, and maintained at this temperature for 3 h with
constant stirring. The analysis of reaction product mixtures
was performed in the presence of internal standard –
n-nonane.
(0.1 mmol) in anhydrous toluene (3 ml) was treated with
PhSiH3 (0.74 ml, 6.0 mmol). The obtained solution was
refluxed for 48 h in a flask with reflux condenser under
argon atmosphere. The solvent was evaporated under
vacuum at room temperature, the residue was dissolved in
CH2Cl2 and diluted with methanol. The precipitate that
formed was filtered off, dissolved in a mixture of ethanol
(10 ml) and tetrahydrofuran (5 ml), and treated with a
solution of 90% KOH (0.32 g, 5.3 mmol) in water (5 ml).
The solution was stirred for 15 h at room temperature. The
organic solvents were evaporated under vacuum, and the
residue was treated with 5 N HCl (20 ml). The precipitate
that formed was filtered off, washed with water (5 ml),
diethyl ether (5 ml), and dried. Yield (including the oxidized
form as impurity) 0.094 g (~70% from compound 16),
0.098 g (~73% from compound 22), white crystals. 1H NMR
spectrum (CD3OD), δ, ppm (J, Hz): 8.01 (2H, s,
H triazole); 8.00 (2H, s, H triazole); 7.38–7.11 (20H, m,
H Ph); 6.82 (4H, d, JPH = 7.8, H Ar); 6.36–6.30 (6H, m,
H Ar); 5.28 (4H, s), 5.26 (4H, s), 5.20 (4H, s) and 5.02
The work was performed with financial support from the
Ministry of Education and Science of the Russian
Federation (Federal target program ''Research and Develop-
ment in the Priority Areas of the Russian Scientific and
Technological Complex for years 2014–2020'', event 1.3,
subsidy contract No. 14.607.21.0083). Unique identifier of
applied scientific research (project) RFMEFI60714X0083.
The authors would like to express their gratitude to
D. A. Cheshkov for help with acquiring DOSY spectra and
interpretation of the obtained results.
References
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2
(4H, s, NCH2, OCH2); 4.19 (4H, d, J = 13.4, ArCH2Ar);
2
2.91 (4H, d, J = 13.4, ArCH2Ar). 31P NMR spectrum
(CD3OD), δ, ppm: –6.6 (P). Found, m/z: 1347.4012 [M–H]–.
C72H61N12O12P2. Calculated, m/z: 1347.4002. Found, m/z:
1363.3922 [M(O)–H]–. C72H61N12O13P2. Calculated, m/z:
1363.3951.
C72H61N12O14P2. Calculated, m/z: 1379.3900.
5-Diphenylphosphanyl-25,26,27,28-tetra(1-carboxy-
methyl-4-triazolylmethoxy)calix[4]arene (25) was
Found,
m/z:1379.3855
[M(O)2–H]–.
prepared analogously to the procedure for obtaining
compound 24 by using calixarene 17 or calixarene 23
(0.15 mmol), PhSiH3 (0.55 ml, 4.5 mmol), toluene (2.5 ml),
90% KOH (0.48 g, 7.7 mmol), ethanol (15 ml),
tetrahydrofuran (7.5 ml), and water (7.5 ml). Yield
(including the oxidized form as impurity) 0.105 g (~60%
from compound 17), 0.118 g (~67% from compound 23),
white crystals. 1H NMR spectrum (CD3OD), δ, ppm (J, Hz):
8.03 (1H, s, H triazole); 8.02 (1H, s, H triazole); 8.00 (2H,
s, H triazole); 7.31–7.26 (2H, m, H Ph); 7.25–7.19 (4H, m,
3
H Ph); 7.01–6.95 (4H, m, H Ph); 6.82 (2H, dd, J = 7.3,
4J = 1.8, H Ar); 6.63–6.60 (2H, m, H Ar); 6.60 (2H, d,
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3J = 7.5, H Ar); 6.57 (2H, dd, 3J = 7.3, 4J = 1.8, H Ar); 6.45
3
(1H, t, J = 7.5, H Ar); 6.44 (2H, d, JPH = 7.8, H Ar); 5.30
(4H, s, NCH2); 5.29 (2H, s, NCH2); 5.25 (2H, s, NCH2);
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2
d, J = 13.4, ArCH2Ar); 4.14 (2H, d, 2J = 13.4, ArCH2Ar);
2
2
3.04 (2H, d, J = 13.4, ArCH2Ar); 2.89 (2H, d, J = 13.4,
31
ArCH2Ar). P NMR spectrum (CD3OD), δ, ppm: –4.8 (P).
Found, m/z: 1165.3741 [M+H]+. C60H54N12O12P. Calculated,
m/z: 1165.3716. Found, m/z: 1181.3695 [M(O)+H]+.
C60H54N12O13P. Calculated, m/z: 1181.3665.
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Catalytic experiments were performed in a 25-ml steel
autoclave that was equipped with a magnetic stirrer and a
thermostat. The autoclave was charged with [Rh(cod)2]BF4
(0.8 mg, 0.002 mmol), 1-octene (0.3 ml, 1.9 mmol), ethyl
alcohol, and the calculated mass of ligand (Table 1). The
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1052

Chemistry of Heterocyclic Compounds 2016, 52(12), 1042–1053
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1053