Synthesis of novel N,O-macrocyclic ligands, functionalized by phosphine oxide groups

Article abstract of DOI:10.1007/s10593-019-02551-0

[Figure not available: see fulltext.] As a result of the implementation of two approaches, the Pudovik reaction (the reaction of macrocyclic azomethines with secondary phosphine oxides) and the Kabachnik–Fields reaction (three-component one-pot process involving dialdehydes, diamines, and secondary phosphine oxides), novel N,O-containing macrocyclic ligands with phosphine oxide groups were first obtained. The synthesized macrocycles are a kind of α-aminophosphoryl compounds that can be used in the synthesis of supramolecular systems.

Full text of DOI:10.1007/s10593-019-02551-0

DOI 10.1007/s10593-019-02551-0
Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
Synthesis of novel N,O-macrocyclic ligands, functionalized
by phosphine oxide groups
1
1
Elena А. Alexandrova , Kristina А. Lotsman ,
2
1
Konstantin А. Lyssenko , Yuri G. Trishin *
1
Higher School of Technology and Energy,
Saint Petersburg State University of Industrial Technologies and Design,
4
Ivana Chernykh St., Saint Petersburg 198095, Russia; е-mail: trish@YT4470.spb.edu
A.N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
8 Vavilova St., Moscow 119991, Russia; е-mail: kostya@ineos.ac.ru
2
2
Translated from Khimiya Geterotsiklicheskikh Soedinenii,
019, 55(9), 875–881
Submitted May 24, 2019
Accepted June 26, 2019
2
As a result of the implementation of two approaches, the Pudovik reaction (the reaction of macrocyclic azomethines with secondary
phosphine oxides) and the Kabachnik–Fields reaction (three-component one-pot process involving dialdehydes, diamines, and secondary
phosphine oxides), novel N,O-containing macrocyclic ligands with phosphine oxide groups were first obtained. The synthesized macro-
cycles are a kind of α-aminophosphoryl compounds that can be used in the synthesis of supramolecular systems.
Keywords: α-aminophosphoryl compounds, N,O-macrocyclic ligands, Kabachnik–Fields reaction, Pudovik reaction.
The synthesis of compounds with high affinity for
various targets and high selectivity for binding to them is
one of the most important tasks of supramolecular
ligands are even more unique in having the so-called
pendant-arms, that is, various functional groups associated
7
8–12
with ring atoms, for example, amine or phosphoryl.
Two phosphorus-containing groups were introduced into
1
chemistry. Such compounds include heteroatomic
8–12
macrocycles, which, due to their special chemical and
physicochemical properties, have found wide application in
macrocycles in a number of studies
via the Pudovik
reaction, the addition of hydrophosphoryl compounds to
two intracyclic C=N bonds. Recently, we presented an
example of the phosphorylation of macrocyclic azomethine
containing four C=N bonds with diphenyl phosphine oxide,
resulting in a ligand with four groups bonded to carbon
2
–5
the creation of host–guest supramolecular systems. One
of the main features of these compounds is the unusual
stability of macrocyclic complexes, known as the
6
macrocyclic effect.
13
An important place among macrocyclic heteroatomic
ligands is occupied by compounds containing both nitrogen
and oxygen atoms in the cycle, which differ in both
electron-donating properties and ability to have different
atoms of the macrocycle. These compounds are referred
to as α-aminophosphoryl compounds due to the presence of
the P(O)CNH group and are known for unique biologically
14
active properties and complex-forming ability. For
example, trivial acyclic α-aminophosphoryl compounds
containing only one P(O)CNH group exhibit high
spatial arrangement (exo- or endodentate) within the
6
macrocyclic structure.
N,O-containing macrocyclic
0
009-3122/19/55(9)-0875©2019 Springer Science+Business Media, LLC
875

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
efficiency and selectivity in the processes of liquid
extraction of metal ions and mineral acids, as well as in the
membrane transport of organic and mineral acid sub-
Scheme 1
O
O
O
14
strates. These properties are largely because of the ability
of the aminophosphoryl group to form a five-membered
chelate structure due to the interaction P=O···H–N. In
macrocyclic aminophosphoryl compounds, these properties
can be significantly enhanced due to a combination of
chelate and macrocyclic effects, which are known to
significantly increase the thermodynamic stability of the
O
O
1
1
H NR NH
2
2
or
CH Cl2
rt, 3–19 h
81–89%
2
1
CH2Cl2, Et3N, EtOH
rt, 11 days 78C, 3 h
99% 92%
H NR NH
(
2
2
2
R ) P(O)H
2
1
5
host–guest complex.
In this work, we synthesized novel N,O-macrocyclic
ligands 3a–d containing phosphine oxide fragments using
two classical methods for the synthesis of α-amino-
phosphoryl compounds, the Pudovik and Kabachnik–Fields
reactions.
R2
R2
O
R2
O
R1
R1
N
N
HN
NH
R2
P
P
2
(
R ) P(O)H
2
CHCl3
2C, 3–4 h
O
O
O
O
6
The N,O-containing macrocyclic compounds 2a,b,
which have a C=N bond in their composition, necessary for
the Pudovik reaction to take place, were obtained by
condensation of dialdehyde 1 with 4,4'-diaminodiphenyl
ether and m-phenylenediamine, respectively (Scheme 1).
The synthesis of macrocyclic azomethine 2a was
previously described and involved the reaction of
dialdehyde 1 with 4,4'-diaminodiphenyl ether upon heating
O
a,b
O
3a–d
86–95%
2
1
1
2
a, 3a–c R = oxybis(4,1-phenylene), 2, 3 d R = m-C H
6
4
2
2
2
3
a,d R = Ph, b R = Bn, c R = Bu
1 1 1
crystallizes in the chiral space group P2 2 2 with one
independent molecule in the unit cell. Its main geometric
parameters are close to those of macrocyclic Schiff base 4
(Fig. 2), in which the oxygen bridge connecting the
benzene rings contains a carbon atom instead of the central
16
in MeOH. However, under the indicated conditions, the
resulting reaction product contains a significant amount of
impurities, and therefore we carried out the reaction in
1
6
CH
2
Cl
2
at 20°С for 10–12 days (control by Н NMR
oxygen atom. In compound 2b, a conformation is realized
spectroscopy monitoring the change in intensity of the
signals of aldehyde proton and protons of the amino
group). The reaction product was obtained with a yield of
in which oxygen atoms have an endodentate arrangement,
and nitrogen atoms, on the contrary, are exodentate. The
geometry of the central macrocyclic fragment in the
molecule 2b is such that all heteroatoms are located in the
same plane with a standard deviation of 0.015 Å. The
distances from oxygen atoms to the geometric center of the
18-membered ring in compound 2b are from 2.74 Å (O(2)
atom) to 2.83 Å (O(1) and O(3) atoms). To compare the
conformations of molecules 2b and 4, it is convenient to
use dihedral angles between the planes of the aromatic
fragments. So, if the values of the angles between rings A
and B, as well as A and C differ slightly, then the
difference in the values of the angles between rings B and
C reaches 20° (Table 1). It should be noted that the
observed changes are most likely not due to the presence of
an additional oxygen atom, but are probably a consequence
of the flexibility of this macrocyclic system and the effect
of crystal packing. Indeed, the calculation of the geometry
of compound 2b in the B3LYP/def-2-TZVP approximation
showed that optimization of the molecule leads to some
flattening of it, in which the value of the dihedral angle
between rings B and C in an isolated molecule is much
closer to the those in compound 4, and the angles between
rings A and B and A and C, on the contrary, are smaller than
in compound 4 and in the crystal of compound 2b. Since this
compound is of interest as a potential ligand, in addition to
analyzing the shape of the molecule, we also calculated the
charges obtained by integrating atomic pools within the
99% (calculated for compound 2a) under the conditions
employed by us, however, the content of the product itself
1
was about 93%, since the H NMR spectrum contains
aldehyde proton signals (~5% of the starting material) and
protons of the NH group (~7% of the starting material).
2
An attempt to isolate compound 2a in a purer form by
recrystallization or using column chromatography did not
lead to success. Therefore, compound 2a was used without
further purification for subsequent phosphorylation. Its
1
13
spectral characteristics (IR, H and C NMR spectra)
1
6
match literature data, while the macrocyclic structure of
the adduct is confirmed by mass spectrometry.
The synthesis of macrocyclic bisazomethine 2b, which
was not previously described in the literature, was carried
out under conditions similar to the preparation of
structurally similar macrocyclic compounds, via the
reaction of dialdehyde 1 with m-phenylenediamine in the
6
3
presence of Et N using absolute EtOH as the solvent.
Composition and structure of compound 2b was confirmed
by elemental analysis, mass spectrometry, IR spectroscopy,
1
13
H, C NMR, and correlation NMR spectroscopy data.
Thus, in the IR spectrum of compound 2b, there is an
–1
absorption band characteristic of the C=N bond at 1687 cm ,
13
and the C NMR spectrum contains a signal of the carbon
atom of this group at 158.7 ppm.
17
The molecular structure of bisazomethine 2b was
determined by X-ray structural analysis (Fig. 1). The
achiral compound 2b, which has close to Сs symmetry,
framework of the quantum theory "Atoms in Molecules".
The charges of oxygen atoms vary in a narrow range –1.09 ÷
–1.04 e, and the charges of nitrogen atoms are –1.16 e. An
8
76

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
Figure 2. The structural formula of macrocyclic Schiff base 4.
Table 1. Dihedral angles between aromatic fragments in com-
pounds 2b and 4
Fragment
Compound
A–B
39.0
46.5
53.1
A–C
39.0
46.5
59.4
B–C
50.8
36.3
56.1
2
b (DFT)
Figure 1. Molecular structure of compound 2b with atoms repre-
sented as thermal vibration ellipsoids of 50% probability.
2
b (solid state)
4
analysis of the crystalline packing showed that, unlike
compound 4, no stacking interactions are observed in
bisazomethine 2b, and all contacts correspond to weak van
der Waals interactions, such as C–Н···О, С–Н···N, and
C–H···π. The greatest number of Н···Н and С–Н···О
interactions is observed between the atoms of the "internal
cavity" of the macrocycle and the hydrogen atoms of the
aromatic ring A.
spectra contain broadened signals of protons of the P(O)CH
groups (5.06–6.14 ppm) and NH groups (4.96–5.20 ppm),
13
while in the C NMR spectra the signals of the carbon
atom of the P(O)CH groups are present (doublets at 47.4–
49.4 ppm, JPС = 63.3–74.8 Hz), which indicates the
addition of secondary phosphine oxides to the C=N bond.
This is also confirmed by the absence of signals of the
carbon atom of the imino group.
The Pudovik reaction, which involves the addition of
hydrophosphoryl compounds to the C=N bond of
azomethines, was carried out by the interaction of
macrocyclic azomethines 2a,b with secondary phosphine
oxides (diphenyl, dibenzyl, and dibutyl phosphine oxides)
We obtained phosphorylated N,O-containing macro-
cyclic ligands 3a–d also by the Kabachnik–Fields reaction,
which is a three-component reaction of dialdehyde 1, the
corresponding diamine (4,4'-diaminodiphenyl ether and
m-phenylenediamine), and secondary phosphine oxide
(diphenyl-, dibenzyl-, and dibutylphosphine oxide) carried
out as a one-pot process. The reaction was carried out in
at a molar ratio of 1:2 by heating in CHCl
Scheme 1). The phosphine oxides used were selected as
3
under reflux
(
14
the most active among hydrophosphoryl compounds. The
reaction progress was monitored by the change in the
intensity of phosphorus atom signals in the P NMR
spectra, namely, by a decrease in the integral intensity of
doublets of hydrophosphoryl compounds at 21.5 ppm,
CH
2 2
Cl at 20°С with the dialdehyde–diamine–phosphine
oxide molar ratio of 1:1:2.1 to almost complete conversion
3
1
1
31
(control by Н and Р NMR spectroscopy). The yields of
final products 3a–d are 81–89%, which practically
coincides with the yields of the same compounds obtained
by the Pudovik reaction. All spectral data of compounds
3a–d synthesized by both the Pudovik reaction and the
Kabachnik–Fields reaction are identical.
JPH = 479.0 Hz (for diphenylphosphine oxide), 36.2 ppm,
JPH = 469.0 Hz (for dibenzylphosphine oxide), and 35.5 ppm,
JPH = 449.0 Hz (for dibutylphosphine oxide), as well as by
the increase in the integral intensity of singlets in the
spectra of the formed phosphorylated macrocyclic
compounds 3a–d.
To conclude, novel N,O-containing macrocyclic
compounds with phosphine oxide groups were obtained as
a result of the implementation of two approaches, the
Pudovik and Kabachnik–Fields reactions. Such ligands can
be used to create supramolecular systems.
Compounds 3a–d, obtained in 86–95% yields, are white
or slightly colored powders, highly soluble in CHCl
CH Cl , poorly soluble in EtOH, PhH, EtOAc, insoluble in
Et O, hexane. The structure of macrocyclic α-amino-
3
,
2
2
Experimental
2
1
13
31
phosphoryl compounds was established using IR, H, C, P
NMR spectroscopy and correlation spectroscopy. The
composition was confirmed by elemental analysis and mass
spectrometry (electrospray ionization). The IR spectra contain
absorption bands of the P=O groups (1144–1169 cm ) and
NH groups (3384–3393 cm ). In the P NMR spectra, the
IR spectra were registered on a Shimadzu FTIR-8400S
1
13
31
spectrophotometer (in CНCl
3
solution). H, C, and
P
NMR spectra were acquired on a Bruker Avance 400
spectrometer (400, 100, and 162 MHz, respectively) in
–
1
1
CDCl
3
, with residual solvent signals (7.26 ppm for H
–
1
31
13
nuclei, 77.0 ppm for C nuclei) as the internal reference.
13
signals at 33.2 ppm (compound 3a), 33.3 ppm (compound
The assignment of signals in C NMR spectra was
verified using spectra recorded in the DEPT mode, as well
as from two-dimensional experiments: H– C HMQC,
3d), 45.5 ppm (compound 3b), and 50.8 ppm (compound 3c)
1
13
have values characteristic of respectively tertiary diphenyl-,
1
1
13
1
1
dibenzyl-, and dibutylalkylphosphine oxides. The H NMR
H– С HMBC, and homocorrelation H– H COSY. For
8
77

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
clarity of the assignment of signals of hydrogen and carbon
atoms, after the description of the spectral data of each
compound, the structural formula with the numbering of
carbon atoms is given in the same way as in published
works. High-resolution mass spectra were recorded on a
Bruker micrOTOF 10223 mass spectrometer (electrospray
0.24 g (99%), yellow glass, mp 104–108°С (mp 95°С
16
–1
(PhMe) ). IR spectrum, ν, cm : 1162 (С–О Alk), 1243
(С–О Ar), 1452, 1496, 1601 (C–C Ar), 1688 (С=N).
1
H NMR spectrum, δ, ppm (J, Hz): 3.94–4.00 (4H, m,
3,18
2 2
9-CH ); 4.21–4.28 (4H, m, 8-CH ); 6.92–7.01 (6H, m,
H-6,12); 7.04–7.05 (2H, m, H-5); 7.17–7.20 (4H, m, H-11);
7.38–7.42 (2H, m, H-4); 8.13–8.16 (2H, m, H-3); 8.94 and
2 2
ionization), eluent MeOH or MeOH–CH Cl . Elemental
13
analysis was performed on a Carlo Erba 1106 Elemental
analyzer, while the content of phosphorus was determined
8.96 (2H, both s, 1-CH). C NMR spectrum, δ, ppm: 68.3
(С-8); 69.8 (С-9); 112.7 (C-6); 119.3 (C-12); 121.5 (C-5);
122.5 (C-11); 125.2 (С-2); 127.6 (C-3); 132.7 (C-4); 147.9
1
9
spectrophotometrically on a Cary-100 apparatus. Melting
points were determined on a PTP(M) apparatus.
(С-10); 155.5 (C-1); 158.6 (С-7,13). Found, m/z: 479.1981
+
2
,2'-Dichlorodiethyl ether ("Glavkhimreaktiv") was
[М+H] . C30
H
27
N
2
O
4
. Calculated, m/z: 479.1965.
purified by distillation. The starting dibenzyl- and dibutyl-
phosphine oxides were obtained by a published procedure:
the reaction of diethylphosphite with the corresponding
2
0
Grignard reagent under an argon atmosphere. Diphenyl-
phosphine oxide was synthesized by hydrolysis of
chlorodiphenylphosphine with 1 N HCl under an argon
21
atmosphere.
1
,7-Bis(2-formylphenyl)-1,4,7-trioxaheptane (1) was
1
6
obtained following a modified literature method.
2 3
K CO
(27.64 g, 0.20 mol) was added to a solution of salicylic
aldehyde (24.42 g, 0.20 mol) in DMF (400 ml), and the
reaction mixture was stirred at 20°С for 30 min. Then a
solution of 2,2'-dichlorodiethyl ether (15.00 g, 0.10 mol) in
DMF (40 ml) was added dropwise. The resulting mixture
was stirred at 150–155°С for 10 h under an argon
atmosphere, then at 20°С for 4 h. As the reaction
progressed, the color of the solution changed from light-
yellow to brown. The dialdehyde was precipitated by
(2E,5E)-8,11,14-Trioxa-3,5-diaza-1,7(1,2),4(1,3)-tri-
benzenacyclotetradecaphane-2,5-diene (2b). A mixture of
dialdehyde 1 (0.48 g, 1.50 mmol), anhydrous EtOH (40 ml),
3
and Et N (0.15 g, 1.50 mmol) was heated to boiling, and a
solution of m-phenylenediamine (0.21 g, 2.00 mmol) in
anhydrous EtOH (20 ml) was added dropwise. The reaction
mixture was heated under reflux for 3 h, then kept at 0–4°С
for 48 h. The formed precipitate was filtered off, dried
2
addition of H O until the color of the solution changed
from dark-brown to light-yellow. The formed mixture was
under reduced pressure, and recrystallized from CH
2 2
Cl .
kept at 0–4°С for 48 h. The formed light-yellow precipitate
Yield 0.53 g (92%), brown needles, mp >240°С. IR spect-
–1
was filtered off, washed with H
EtOH, and dried under reduced pressure. Yield 21.7 g
2
O, recrystallized from
rum, ν, cm : 1247 (С–О Ar), 1452, 1487, 1601 (C–C Ar),
1
1687 (С=N). H NMR spectrum, δ, ppm (J, Hz): 3.90–3.92
(
(
69%), beige needles, mp 72–73°С (EtOH) (mp 75–76°С
2 2
(4H, m, 9-CH ); 4.25–4.27 (4H, m, 8-CH ); 6.90 (2H, d,
16
18
22
EtOH), mp 59–61°С (Me
2
CO), mp 73°С (CHCl
3
),
J = 8.2, H-6); 7.00 (1H, s, H-13); 7.04 (2H, t, J = 7.5, H-5);
7.27 (2H, dd, J = 7.8, J = 1.7, H-11); 7.39–7.44 (3H, m,
H-4,12); 8.20 (2H, dd, J = 7.8, J = 1.4, H-3); 9.22 (2H, s,
2
3
1
mp 73.5°С (MeOH) ). H NMR spectrum, δ, ppm (J, Hz):
.99–4.02 (4H, m, 9-CH ); 4.27–4.30 (4H, m, 8-CH ); 7.00
2H, d, J = 8.3, H-6); 7.04 (2H, t, J = 7.5, H-5); 7.54 (2H,
3
(
2
2
13
1-CH). C NMR spectrum, δ, ppm: 67.2 (С-8); 70.8 (С-9);
109.6 (C-13); 111.2 (C-6); 121.2 (C-11); 121.4 (C-5);
124.2 (С-2); 127.2 (C-3); 129.2 (C-12); 133.1 (C-4); 154.7
td, J = 7.8, J = 1.8, H-4); 7.83 (2H, dd, J = 7.7, J = 1.6,
H-3); 10.51 (2H, s, 1-CH).
(
С-10); 158.7 (С-1); 159.0 (С-7). Found, m/z: 387.1717
+
23 2 3
[М+H] . C24H N O . Calculated, m/z: 387.1703. Found, %:
O
O
O
С 74.44; Н 5.56; N 7.28. C24
С 74.59; Н 5.74; N 7.25.
22 2 3
H N O . Calculated, %:
3
6
2
7
1
4
5
O
8
O
9
1
2
,7,10,13-Tetraoxa-4,16-diaza-1,3(1,4),6,14(1,2)-tetra-
benzenacyclohexadecaphane-4,15-diene (2a). A solution
of dialdehyde 1 (0.16 g, 0.50 mmol) in CH Cl (10 ml) was
added dropwise with stirring to a solution of 4,4'-diamino-
diphenyl ether (0.10 g, 0.50 mmol) in CH Cl (40 ml). The
2
2
2
2
reaction mixture was stirred at 20°С for 11 days. The
Synthesis of compounds 3a–d by the Pudovik reaction
solvent was evaporated under reduced pressure. Yield
(General method). The corresponding phosphine oxide
8
78

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
(
3
0.50 mmol) in CHCl (5 ml) was added to compound 2a or
2
b (0.25 mmol) under an argon atmosphere. The reaction
mixture was heated under reflux for 3–4 h. The solvent
was evaporated under reduced pressure. For compounds
3
3
a,b,d, the residue was recrystallized, while for compound
c, it was washed with hot Et O.
,7,10,13-Tetraoxa-4,16-diaza-1,3(1,4),6,14(1,2)-tetra-
2
2
benzenacyclohexadecaphane-5,5-diylbis(diphenylphos-
phine oxide) (3a). Yield 147 mg (86%), white powder,
–1
mp 166–170°С (PhH). IR spectrum, ν, cm : 1120 (С–О Alk),
169 (Р=O), 1242 (С–О Ar), 1452, 1500, 1600 (C–C Ar),
1
1
3
393 (NH). H NMR spectrum, δ, ppm (J, Hz): 3.42–3.44
2H, m, 8-CH ); 3.74–3.75 (4H, m, 9-CH ); 3.86–3.87 (2H,
m, H-8'); 5.20 (2H, br. s, NH); 5.79 (2H, d, J = 10.1, 1-СН);
2,7,10,13-Tetraoxa-4,16-diaza-1,3(1,4),6,14(1,2)-tetra-
benzenacyclohexadecaphane-5,15-diylbis(dibutylphos-
phine oxide) (3c). Yield 283 mg (95%), beige powder,
(
2
2
–
1
6
6
.35 (2H, t, J = 9.0, H-6); 6.46–6.54 (8H, m, H-11,12); 679–
.84 (2H, m, H-5); 6.95–6.96 (2H, m, H-4); 7.05–7.31
mp 130–145°С. IR spectrum, ν, cm : 1144 (Р=O), 1238
(С–О Ar), 1452, 1499, 1600 (C–C Ar), 3385 (NH).
1
(
(
16H, m, H-15,16); 7.50–7.54 (2H, m, H-3); 7.85–7.86
4H, m, H-17). C NMR spectrum, δ, ppm (J, Hz): 49.4 (d,
H NMR spectrum, δ, ppm (J, Hz): 0.70–0.75 (6H, m,
13
17-CH
15,16-CH
m, 14'-CH
8-CH ); 5.06–5.07 (4H, m, NH, 1-CH); 6.49–6.51 (4H, m,
3
); 0.87–0.91 (6H, m, 17'-CH
); 1.55–1.58 (4H, m, 14-CH
); 3.92–3.94 (4H, m, 9-CH ); 4.14–4.17 (4H, m,
3
); 1.13–1.45 (16H, m,
J = 67.1, C-1); 66.7 (С-8); 70.0 (С-9); 110.4 (C-6); 114.5
C-12); 119.5 (C-11); 121.5 (C-5); 124.2 (С-2); 127.5;
28.8; 131.5; 131.6; 131.7; 132.2 (C-3,4,15–17); 132.7
2
2
); 1.87–1.89 (4H,
(
1
2
2
2
3
1
(
С-14); 142.0 (С-10); 150.1 (С-13); 155.5 (C-7). P NMR
H-12); 6.53–6.54 (4H, m, H-11); 6.75–6.77 (2H, m, H-6);
6.87–6.90 (2H, m, H-5); 7.10–7.14 (2H, m, H-4); 7.43–
7.44 (2H, m, H-3). C NMR spectrum, δ, ppm (J, Hz):
13.6; 13.8 (С-17); 23.1; 24.3; 24.4 (С-15,16); 25.3 (d,
J = 65.2, C-14); 27.4 (d, J = 65.2, C-14'); 48.5 (d, J = 63.3,
C-1); 67.4 (C-8); 70.0 (C-9); 110.8 (C-6); 114.5 (C-12);
+
spectrum, δ, ppm: 33.2. Found, m/z: 905.2908 [М+Na] .
NaO . Calculated, m/z: 905.2880. Found, %:
13
C
H N
54 48 2
6
Р
2
С 73.32; Н 5.32; N 3.30; Р 7.32. C54
Calculated, %: С 73.46; Н 5.48; N 3.17; Р 7.02.
48 2 6 2
H N O Р .
1
19.4 (C-11); 122.0 (C-5); 125.0 (C-2); 128.8 (C-3); 129.0
31
(
C-4); 142.0 (C-10); 150.1 (C-13); 155.6 (C-7). P NMR
+
spectrum, δ, ppm: 50.8. Found, m/z: 825.4132 [М+Na] .
NaO . Calculated, m/z: 825.4132. Found, %:
C
46
H
64
N
2
6 2
Р
С 68.60; Н 8.05; N 3.32; Р 7.59. C46
Calculated, %: С 68.81; Н 8.03; N 3.49; Р 7.71.
64 2 6 2
H N O Р .
1
2
1
7
1
3 O
Me
1
6
1
11
Me
1
0
4
1
5
NH
HN
O
O
1
P
P
4
,16-Diaza-1,3(1,4),6,14(1,2)-tetrabenzena-2,7,10,13-
Me
2
Me
3
tetraoxacyclohexadecaphane-5,15-diylbis(dibenzylphos-
4
phine oxide) (3b). Yield 205 mg (87%), beige powder,
7 O
8
O
5
–
1
6
mp 154–161°С (EtOH). IR spectrum, ν, cm : 1130 (С–О
Alk), 1165 (Р=O), 1240 (С–О Ar), 1454, 1498, 1601 (C–C
O
9
1
3c
Ar), 3384 (NH). H NMR spectrum, δ, ppm (J, Hz): 2.69–2.83
(
4H, m, H-14); 3.16 (2H, t, J = 14.0, H-14'); 3.34 (2H, t,
J = 13.7, H-14''); 3.62–3.66 (4H, m, 9-CH ); 4.02–4.03
); 5.15–5.16 (4H, m, NH, 1-CH); 6.41–6.43
4H, m, H-12); 6.58–6.60 (4H, m, H-11); 6.69–6.71 (2H,
2
(
(
4H, m, 8-CH
2
8,11,14-Trioxa-3,5-diaza-1,7(1,2),4(1,3)-tribenzenacyclo-
tetradecaphane-2,6-diylbis(diphenylphosphine oxide) (3d).
Yield 174 mg (88%), light-brown powder, mp 176–186°С
(PhH). IR spectrum, ν, cm : 1121 (С–О Alk), 1169 (Р=O),
1247 (С–О Ar), 1452, 1490, 1604 (C–C Ar), 3388 (NH).
1H NMR spectrum, δ, ppm (J, Hz): 3.37–3.40 (2H, m,
m, H-6); 6.89–6.93 (2H, m, H-5); 7.06–7.20 (22H, m,
1
3
–1
H-4,16–18); 7.46–7.47 (2H, m, H-3). C NMR spectrum,
δ, ppm (J, Hz): 32.0 (d, J = 61.4, C-14); 34.7 (d, J = 61.4,
C-14'); 47.4 (d, J = 63.3, C-1); 67.2 (C-8); 69.8 (C-9); 110.9
(
1
C-6); 114.5 (C-12); 119.4 (C-11); 122.1 (C-5); 124.2 (C-2);
27.0; 128.6; 128.7; 129.2; 130.0; 130.1 (C-3,4,16–18); 131.4;
8-CH
8'-CH
2
); 3.47–3.52 (2H, m, 9-CH ); 3.82–3.87 (2H, m,
2
); 3.90–3.94 (2H, m, 9'-CH ); 4.96–5.00 (2H, m,
2
2
1
32.4 (C-15,15'); 141.9 (C-10); 150.3 (C-13); 155.7 (C-7).
NH); 6.03 (2H, dd, J = 7.8, J = 2.0, H-11); 6.08–6.14 (1H,
m, 1-CH); 6.29 (1H, s, H-13); 6.52 (2H, d, J = 8.2, H-6);
6.75 (1H, t, J = 7.9, H-12); 6.97 (2H, t, J = 7.5, H-5); 7.15–
7.19 (6H, m, H-15); 7.29–7.39 (10H, m, H-15',16); 7.46
(2H, t, J = 7.5, H-4); 7.54 (2H, d, J = 7.6, H-3); 7.74 (2H,
3
1
P NMR spectrum, δ, ppm: 45.5. Found, m/z: 961.3526
+
[
М+Na] . C58
H
56
N
2
NaO
6
Р
2
. Calculated, m/z: 961.3506.
Found, %: С 73.96; Н 6.06; N 2.99; Р 6.94. C58
Calculated, %: С 74.19; Н 6.01; N 2.98; Р 6.60.
56 2 6 2
H N O Р .
8
79

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
1
3
25
d, J = 7.6, H-17); 7.76 (2H, d, J = 7.6, H-17'). C NMR
spectrum, δ, ppm (J, Hz): 47.8 (d, J = 74.8, C-1); 67.7
(
1
1
Gaussian 09
program 2 using empirical dispersion
6
correction of total energy and Becke–Jonson damping
(DFT-D3) . Topological analysis of theoretically calcu-
lated function ρ(r) was done by AIMAll programm.
27
C-8); 69.7 (C-9); 96.0 (C-13); 107.1 (C-11); 110.3 (C-6);
21.6 (C-5); 124.5 (C-2); 127.6; 127.7 (C-15); 128.7;
28.8; 128.9 (C-16); 129.0 (C-12); 129.6 (C-3); 130.7
C-14); 131.6; 132.0 (C-4,17); 147.4 (C-10); 156.0 (C-7).
P NMR spectrum, δ, ppm: 33.3. Found, m/z: 791.2791
28
References
(
3
1
1
. Park, H. S.; Lin, Q.; Hamilton, A. D. J. Am. Chem. Soc. 1999,
+
1
21, 8.
[
М+H] . C48
H
45
N
2
O
5
Р
2
. Calculated, m/z: 791.2798. Found,
2
3
. Tabushi, I.; Yamamura, K. Top. Curr. Chem. 1983, 113, 146.
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44 2 2 5
H Р N O .
Calculated, %: С 72.90; Н 5.61; N 3.54; Р 7.83.
4
. Erkin, A. V.; Gurzhiy, V. V.; Krutikov,V. I. Chem.
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Synthesis of compounds 3a–d by the Kabachnik–Fields
reaction (General method). A solution of compound 1
9. Bilge, S.; Nadzagdorj, A.; Akduran, N.; Hokelek, T.; Kilic, Z.
(
0.31 g, 1.0 mmol) in CH
with stirring under argon atmosphere to a solution of
,4'-diaminodiphenyl ether or m-phenylenediamine
1.0 mmol) in CH Cl (30 ml). Then a solution of
phosphine oxide (2.1 mmol) in CH Cl (7 ml) was added
2
Cl
2
(5 ml) was added dropwise
J. Mol. Struct. 2002, 611, 169.
1
1
0. Ilter, E. E.; Kilic, Z. Spectrochim. Acta, Part A 2008, 70, 542.
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4
(
2
011, 81, 441.
2
2
1
1
2. Kocak, S. B.; Uckardes¸ H. Heteroat. Chem. 2012, 23, 583.
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2
2
dropwise; the reaction mixture became bright-yellow. The
reaction mixture was stirred at 20°С for 3–19 h. The
solvent was evaporated under reduced pressure.
Purification of the obtained compounds was carried out in
the same way as in their synthesis by the Pudovik reaction.
Yields of compounds: 3a – 756 mg (86%), 3b – 811 mg
2
345. [Zh. Obshch. Khim. 2013, 83, 2062.]
14. Cherkasov, R. A.; Galkin, V. I. Russ. Chem. Rev. 1998, 67,
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15. Stid, Dzh. V.; Etvud, Dzh. L. Supramolecular Chemistry
[
Russian translation]; IKTs "Akademkniga": Moscow, 2007,
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(
86%), 3c – 718 mg (89%), 3d – 643 mg (81%).
1
1
1
6. Kedy, S.; Almhna, N.; Kandil, F. Jordan J. Chem. 2012,
X-ray structural analysis of single crystals of
compound 2b was performed on a Bruker APEX II CCD
diffractometer (λ(MoKa) 0.71072 Å, ω-scanning,
7
, 73.
7. Beider, R. Atoms in Molecules. A Quantum Theory [Russian
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2
ϴ < 58°). Single crystals of compound 2b were obtained
–1
3 22 2 3
from CHCl solution (C24H N O , M 386.43, μ 0.87 cm ,
d
–3
calc 1.303 g·cm ); they are rhombic (at 120 K), space
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symmetry group P2 ; a 8.3883(4), b 10.6916(5),
1 1 1
2 2
3
c 21.9716(10) Å; V 1970.5(16) Å . A total of 23556
reflections were collected; 5248 independent reflections
(Rint 0.02920) were used in further refinement. The
2
0. Keglevich, G.; Jablonkai, E.; Balazs, L. B. RSC Adv. 2014, 4,
2808.
2
structure was solved with the direct method and refined
2
1. Kabat, M. M.; Garofalo, L. M.; Daniewski, A. R.;
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2
against Fhkl by the least-squares technique in the full-
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The final probability factor values: wR
2
0.1041 and GOF
0.0385 were
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1
.009 for all independent reflections (R
1
2
4. Sheldrick, G. M. SHELXTL v.6.14. Structure Determination
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All calculations were performed using the SHELXTL
2
5. Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.;
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24
software package. The full set of X-ray structural data
and atomic coordinates were deposited at the Cambridge
Crystallographic Data Center (deposit CCDC 1907415).
Optimization of an isolated molecule 2b carried out by
the density functional method (B3LYP/def-2-TZVP) in
8
80

Chemistry of Heterocyclic Compounds 2019, 55(9), 875–881
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8
81