New calix[4]resorcinols with thiophosphoryl-containing fragments

Article abstract of DOI:10.1080/10426507.2011.554926

The condensation of thiophosphorylated aldehydes 1 and 2 with resorcinol and its derivatives leads to the formation of the new type of calix[4]resorcinols with four thiophosphoryl groups inserted to the substituents located in methylidene bridges of the m

Full text of DOI:10.1080/10426507.2011.554926

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New Calix[4]Resorcinols with
Thiophosphoryl-Containing Fragments
Irina R. Knyazeva a , Alexander R. Burilov a , Guzyal M. Fazleeva a ,
Il’dus A. Nuretdinov a , Tatyana V. Gryaznova a , Yulia G. Budnikova
a , Vera V. Khrisanforova a , Aidar T. Gubaidullin a , Bulat M.
Gabidullin a , Victor V. Syakaev a , Michael A. Pudovik a & Alexander
I. Konovalov a
a A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Center , Russian Academy of Sciences , Kazan, Russian
Federation
Published online: 24 Aug 2011.
To cite this article: Irina R. Knyazeva , Alexander R. Burilov , Guzyal M. Fazleeva , Il’dus A.
Nuretdinov , Tatyana V. Gryaznova , Yulia G. Budnikova , Vera V. Khrisanforova , Aidar T. Gubaidullin ,
Bulat M. Gabidullin , Victor V. Syakaev , Michael A. Pudovik & Alexander I. Konovalov (2011) New
Calix[4]Resorcinols with Thiophosphoryl-Containing Fragments, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:9, 1972-1980, DOI: 10.1080/10426507.2011.554926
To link to this article: http://dx.doi.org/10.1080/10426507.2011.554926
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Phosphorus, Sulfur, and Silicon, 186:1972–1980, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.554926
NEW CALIX[4]RESORCINOLS WITH
THIOPHOSPHORYL-CONTAINING FRAGMENTS
Irina R. Knyazeva, Alexander R. Burilov, Guzyal M. Fazleeva,
Il’dus A. Nuretdinov, Tatyana V. Gryaznova, Yulia G.
Budnikova, Vera V. Khrisanforova, Aidar T. Gubaidullin,
Bulat M. Gabidullin, Victor V. Syakaev, Michael A. Pudovik,
and Alexander I. Konovalov
A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific
Center, Russian Academy of Sciences, Kazan, Russian Federation
GRAPHICAL ABSTRACT
Abstract The condensation of thiophosphorylated aldehydes 1 and 2 with resorcinol and its
derivatives leads to the formation of the new type of calix[4]resorcinols with four thiophos-
phoryl groups inserted to the substituents located in methylidene bridges of the molecule. The
conformation of these compounds was found to be “flattened partial cone” or “chair,” which
was determined by NMR methods and a single-crystal X-ray diffraction study.
Keywords Calix[4]resorcinol; condensation; thiophosphorylated aldehyde; conformation
INTRODUCTION
The chemistry of calixarenes with organoelement fragments, especially with
phosphorus-containing functional groups, attracts a great interest of many scientists of the
world due to their ability to form complexes with various organic molecules and metal
Received 13 December 2010; accepted 12 January 2011.
The work was supported by the Russian Foundation for Basic Research (grant no. 08-03-00512a).
Address correspondence to Irina R. Knyazeva, A. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Scientific Center, Russian Academy of Sciences, Arbuzov Street 8, 420088 Kazan, Russian Federation.
E-mail: ihazieva@mail.ru
1972

CALIX[4]RESORCINOLS WITH THIOPHOSPHORYL-CONTAINING FRAGMENTS 1973
ions, tendency toward self-assembly, which leads to the formation of supramolecular
ensembles. Set of the above mentioned properties makes this compound class promising
for the creation of new types of complexing agents,1 metal ion extraction agents,2 and
catalytic systems.3–5
The general pathway to the synthesis of calix[4]resorcinols is based on the acidic con-
densation of resorcinol and aldehydes.6,7 In order to develop this method, we have recently
obtained new calix[4]resorcinols bearing phosphonates and phosphonium fragments on the
lower rim of the molecule using phosphorylated derivatives of benzaldehyde as reactants.8,9
In the present study, we synthesized the first representatives of calix[4]resorcinols
with four thiophosphoryl (P S) groups inserted to the substituents located in the methyli-
dene bridges of the molecule. It is known that the P S group actively interacts with salts
of different metals10 and alkyl halides.11 In addition, while phosphonate (P O) derivatives
have proved to be efficient extractants for hard cationic species,12,13 for thiophosphonate
(P S) derivatives the different and interesting properties toward soft metal cations may be
expected.
RESULTS AND DISCUSSION
Thiophosphorylated aldehydes 1 and 2 with the aromatic spacer between thiophos-
phoryl and aldehyde groups (thiophosphoryl group located in para or meta positions in
relation to the aldehyde fragment) were used as new starting materials for the synthesis of
calixarenes. New thiophosphorylated calix[4]resorcinols 3a–c and 4a–c were obtained by
the condensation of these aldehydes with resorcinol, 2-methylresorcinol, and pyrogallol in
acidic aqueous alcoholic media after prolonged heating (Scheme 1).
Scheme 1
1
31P, H, 13C, electrospray ionization (ESI) mass spectra, and elemental analysis are
in a good agreement with the proposed structure. The presence of only one signal at
approximately 62 ppm in the 31P NMR spectrum of each from obtained compounds indicates
that the four phosphorus atoms are equivalent.
Several conformations with different arrangements of resorcinol rings and sub-
stituents in the methylidene bridges with respect to each other and to the macrocycle

1974
I. R. KNYAZEVA ET AL.
plane are known for calix[4]resorcinols to be as cone, flattened cone, flattened partial cone,
1,2-alternate, and 1,3-alternate.14 The preferred conformation of a structure depends on
the properties of the introduced functional groups, the nature of the substituent groups in
the calixarene matrix, and the reaction conditions.
The calix[4]resorcinol 4b crystallized in the triclinic crystal system, space group
P-1, forms a crystal solvate with two water molecules and four dimethylformamide (DMF)
molecules per calixarene macrocycle. The calixarene molecule occupies a special position
and has an inversion center. One of the DMF molecules and one of the thiophosphoryl-
containing substituents are disordered in the crystal over two positions with relative occu-
pancies 0.65:0.35 and 0.60:0.40, respectively. The calix[4]resorcinol 4b molecule has rctt
configuration of its thiophosphoryl-containing substituents and exists in “chair” conforma-
tion (Figure 1). The selected bond lengths and angles around the phosphorus atoms are in
Figure 1 Two different views of the molecule 4b and partial numbering scheme, hydrogen atoms, and solvate
molecules of water and DMF are omitted for clarity. Disordered thiophosphoryl-containing substituents (P1) are
shown in the position with the greater occupancy. The selected bond lengths (Å) and angles (◦) are P1 O31A
1.542(7), P1 O1A 1.559(7), P1 O20 1.570(5), P1 S1A 1.889(7), P2 O5 1.519(6), P2 O6 1.551(7), P2 O25 1.554(5),
P2 S2 1.899(4); O5 P2 O6 98.6(4), O5 P2 O25 102.5(3), O6 P2 O25 101.9(4), O5 P2 S2 118.7(3), O6 P2 S2
117.0(3), O25 P2 S2 115.3(2), C35 O5 P2 125.9(8).

CALIX[4]RESORCINOLS WITH THIOPHOSPHORYL-CONTAINING FRAGMENTS 1975
Figure 2 1H NMR spectrum of calix[4]resorcinol 3b (600 MHz, DMSO-d6).
the range of the typical values for thiophosphates and are presented in the description of
Figure 1. Two opposite resorcinol rings are coplanar and the other two are antiparallel.
All hydroxyl groups of the calixresorcinol scaffold take part in the classical hydrogen
bonding interactions with the solvate molecules. Calixarene macrocycles are connected by
hydrogen bonds through water molecules and by π–π interaction, forming supramolecular
pillars along crystallographic axis Ox. Due to the nonclassical hydrogen bond interactions,
those pillars generate layers parallel to Oxy crystallographic plane.
The presented results of the single-crystal X-ray diffraction analysis are in agreement
1
with the NMR spectroscopic data for all obtained compounds. The Н and 13C NMR
spectra of compounds 3а–с and 4а–с display the duplication of signals from protons and
carbon atoms of resorcinol fragments (Figure 2). This attests to the different (vertical and
horizontal) arrangements of opposite resorcinol rings with respect to the macrocycle plane.
1
The NMR H 2D NOESY spectrum of compound 3b (Figure 3) shows the cross-peak
between signals of protons of methyl groups from vertically oriented 2-methylresorcinol
v
fragments (CH3 ), and signals of aromatic protons from substituent in the methylidene
bridges (Ph). This indicates that the molecule exists in “flattened partial cone” (or “chair”)
conformation.
EXPERIMENTAL
1H and 13C NMR spectra were recorded on a Bruker AVANCE-600 spectrometer
(600 and 150 MHz, respectively) in dimethyl sulfoxide (DMSO)-d6 or acetone-d6; 31Р
NMR spectra were recorded on a Bruker MSL-400 NMR-Fourier spectrometer (166.93
MHz). NMR experiments were carried out in solutions (10 mmol × L−1) at 303 K. The
pulse programs of the 2D NOESY experiments were taken from Bruker software library.
IR spectra were measured on a Bruker Vector 22 Fourier-transform spectrometer; the solid
samples were examined as emulsions in Vaseline. ESI mass spectra were recorded on
Esquire-LC 00084 instrument.

1976
I. R. KNYAZEVA ET AL.
Figure 3 Fragment of 1H NMR 2D NOESY spectrum for compound 3b (600 MHz, DMSO-d6).
X-Ray Crystallography
Suitable single crystals were obtained from a solution of 4b in DMF at
ambient temperature. The X-ray diffraction data for crystal of compound 4b,
C72H84O20P4S4·4C3H7NO·2H2O, were collected at 296 K on a Bruker AXS Smart
Apex II CCD diffractometer in the ω and φ-scan modes using graphite monochromated
MoKα (λ 0.71073Å) radiation. The crystal data, data collection, and the refinement
are given in Table 1. Data were corrected for the absorption effect using SADABS
program.15 The structures were solved by a direct method and refined by the full matrix
least squares using SHELXTL16 and WinGX17 programs. All nonhydrogen atoms were
refined anisotropically. The positions of hydrogen atoms were located from the Fourier
electron density synthesis and were included in the refinement in the isotropic riding model
approximation.
Data Collections. Images were indexed, integrated, and scaled using the APEX218
data reduction package. All figures were made using PLATON.19
Crystallographic data (excluding structure factors) for the structure 4b in this pa-
per have been deposited with the Cambridge Crystallographic Data Centre as supple-
mentary publication number CCDC 803752. Copies of the data can be obtained free of
charge, on application to CCDC, 12 Union Road, Cambridge CB2 1EZ, UK (E-mail:
deposit@ccdc.cam.ac.uk).
Diethyl-(4-formylphenyl)thiophosphate 1 was synthesized according to a known
procedure.20
Diethyl-(3-formylphenyl)thiophosphate 2. A solution of 3-hydroxybenzaldehyde
(2.1 g, 0.017 mol) in tetrahydrofuran (THF) (25 mL) was added dropwise to the suspension

CALIX[4]RESORCINOLS WITH THIOPHOSPHORYL-CONTAINING FRAGMENTS 1977
Table 1 Crystallographic data for calix[4]resorcinol 4b
Empirical formula
Compound formula
Formula mass
Temperature (K)
Crystal size (mm)
Crystal description
Crystal system
Space group
a (Å)
C84H116N4O26P4S4
C72H84O20P4S4·4C3H7NO·2H2O
1849.93
296(2)
0.13 × 0.16 × 0.28
Pink prism
Triclinic
P − 1
9.1242(12)
16.020(2)
b (Å)
c (Å)
16.550(2)
97.343(2)
94.394(2)
97.763(2)
α (◦)
β (◦)
γ (◦)
V (Å3)
2366.4(5)
Z
1
ρcalc (g/cm3)
1.298
2.42
980
1.92 – 26.25
−11 ≤ h ≤ 11
−19 ≤ k≤ 19
−20 ≤ l ≤ 20
18338
µ (cm−1
F(000)
θ range (◦)
)
Index ranges
Reflections collected
Reflections observed (I > 2σ)
Reflections unique
R1, wR2 (2σ data)
3482
9337 (Rint = 0.0581)
0.0812, 0.2004
0.2092, 0.2714
0.9353/0.9692
9337/36/586
0.950
R1, wR2 (all data)
Max/min transmission factors
Data/restraints/parameters
GooF on F2
Largest difference electron density peak/hole (e/Å3)
0.386/− 0.239
of NaH (0.5 g, 0.0208 mol) in THF (50 mL) at 10 ◦С and reaction mixture was stirred at room
temperature for 40 min. Then, the solution of diethylthiophosphoric acid chloroanhydride
(3 g, 0.016 mol) in THF was added and the mixture was stirred at room temperature for 12 h.
The reaction mixture was quenched with H2O and extracted with benzene (5 × 25 mL).
After drying over MgSO4 and removal of the solvent by evaporation, the crude product
was purified by column chromatography using a mixture of n-hexane/ethyl acetate (3:1) as
eluent. The desired product was obtained as light yellow oil (3.02 g, 69% yield, Rf = 0.58).
31Р NMR (166.93 MHz, acetone-d6): δ = 61.5 ppm. 1Н NMR (600 MHz, acetone-d6): δ =
1.37 (t, 3JHH = 6.97 Hz, 6Н, СН3), 4.29 (m, 4Н, ОСН2), 7.54 (d, 3JHH = 8.07 Hz, 1Н,
СНar), 7.64 (t, 3JHH = 7.70 Hz, 1Н, СНar), 7.74 (s, 1Н, СНar), 7.82 (d, 3JHH = 7.70 Hz,
1Н, СНar,), 10.07 (s, 1Н, СНО) ppm. IR (film) νmax: 822 (P S); 973, 1023 (P O C)
cm−1. Anal. Calcd. for C11H15O4PS: C, 48.17; H, 5.51; P, 11.29; S, 11.69. Found: C, 48.21;
H, 5.34; P, 11.49; S, 11.54.
Calix[4]resorcinol 3а. The mixture of resorcinol (0.31 g, 2.82 mmol) and aldehyde
1 (0.77 g, 2.82 mmol) in ethanol (6 mL), water (6 mL), and concentrated hydrochloric
acid (2 mL) was stirred under heating at 70 ◦С for 3 days. The precipitate was filtered and
washed with ethanol and diethyl ether. After drying in vacuo (40 ◦С, 0.06 Torr), the product

1978
I. R. KNYAZEVA ET AL.
was obtained (0.60 g, 58%) as white powder. mp > 220 ◦С (dec.). 31Р NMR (166.93 MHz,
DMSO-d6): δ = 62.3 ppm. 1H NMR (600 MHz, DMSO-d6): δ = 1.31 (m, 24Н, CH3), 4.17
(m, 16Н, CH2), 5.50 (s, 2Н, H4h), 5.54 (s, 4H, CH), 6.16 (s, 2Н, H4v), 6.17 (s, 2Н, H1v),
3
3
6.33 (s, 2Н, H1h), 6.61 (d, JHH = 8.59 Hz, 8Н, CH Car CHar), 6.71 (d, JHH = 8.59
Hz, 8Н, O Car CHar), 8.58 (s, 4Н, ОHv), 8.63 (s, 4Н, ОHh) ppm. 13C NMR (150 MHz,
d6-DMSO): δ = 15.7 (s, CH3), 41.4 (s, CH), 64.6 (s, CH2), 101.8 (s, C1v), 101.9 (s, C1h),
119.2 (s, CHar), 119.5 (s, C4v), 120.5 (s, C3v), 120.8 (s, C3h), 129.9 (s, CHar), 131.4 (s,
C4h), 141.3 (s, Car), 147.5 (с, Car), 150.7 (s, C2h), 152.9 (s, C2v) ppm. IR νmax: 830 (P S);
956, 1016 (P O C); 3150–3550 (ОН) cm−1. Anal. Calcd. for С68Н76O20P4S4: С, 55.74;
Н, 5.19; P, 8.47; S, 8.74. Found: С, 54.68; Н, 5.22; P, 8.20; S, 8.63. ESI-MS: m/z = 1465
[M+H]+ (calcd. M = 1464).
Calix[4]resorcinol 3b. This compound was obtained as white powder by a method
analogous to that used to prepare 3a by treatment of 2-methylresorcinol (0.24 g, 1.93 mmol)
◦
with aldehyde 1 (0.53 g, 1.93 mmol). Yield 0.4 g (65%), mp > 255 С (dec.). 31Р NMR
1
(166.93 MHz, DMSO-d6): δ = 62.4 ppm. H NMR (600 MHz, DMSO-d6): δ = 1.31 (t,
3JHH 6.7 Hz, 24H, CH3), 1.93 (s, 6Н, H5h), 2.07 (s, 6Н, H5v), 4.18 (m, 16H, CH2), 5.27 (s,
2Н, H4h), 5.62 (s, 4H, CH), 6.11 (s, 2Н, H4v), 6.63 (d, 3JHH = 8.4 Hz, 8Н, CH Car CHar),
6.69 (d, JHH = 8.4 Hz, 8Н, O Car CHar), 7.43 (s, 4Н, ОHv), 7.69 (s, 4Н, ОHh) ppm.
3
13C NMR (150 MHz, d6-DMSO): δ = 9.6 (s, C5h), 10.1 (s, C5v), 15.8 (d, JСР = 5.8
3
Hz, CH3), 43.1 (s, СH), 64.7 (d, JСР = 5.8 Hz, CH2), 110.9 (s, C1h), 111.1 (s, C1v),
2
119.4 (d, 3JСР = 3.0 Hz, P O Car CHar), 122.0 (s, C3v), 122.8 (s, C3h), 125.6 (s, C4v),
127.8 (s, C4h), 130.4 (s, CH Car CHar), 140.5 (s, CH Car), 147.8 (d, JСР = 7.5 Hz,
2
P O Car), 150.6 (s, C2h), 150.7 (s, C2v) ppm. IR νmax: 818 (P S); 942, 1020 (P O C);
3150–3650 (ОН) cm−1. Anal. Calcd. for С72Н84O20P4S4: С, 56.80; Н, 5.53; P, 8.16; S,
8.42. Found: С, 56.77; Н, 5.52; P, 7.84; S, 8.48. ESI-MS: m/z = 1521 [M+H]+ (calcd. М =
1520).
Calix[4]resorcinol 3c. This compound was obtained as dark pink powder by a method
analogous to that used to prepare 3a by treatment of pyrogallol (0.46 g, 3.65 mmol) with
aldehyde 1 (1.00 g, 3.65 mmol). Yield 0.84 g (60%), mp > 180 ◦С (dec.). 31Р NMR (166.93
MHz, acetone-d6): δ = 61.5 ppm. 1H NMR (600 MHz, acetone-d6): δ = 1.37 (t, 3JHH = 7.3
Hz, 24H, CH3), 4.26 (m, 16H, CH2), 5.34 (s, 2Н, H4h), 5.80 (s, 4H, CH), 6.11 (s, 2Н, H4v),
6.76 (d, 3JHH = 8.4 Hz, 8Н, CH Car CHar), 6.84 (d, 3JHH = 8.4 Hz, 8Н, O Car CHar),
8.01 (s, 12Н, ОH) ppm. IR νmax: 819 (P S); 926, 1020 (P O C); 3250–3600 (ОН) cm−1
.
Anal. Calcd. for С68Н76O24P4S4: С, 53.40; Н, 4.97; P, 8.12; S, 8.38. Found: С, 53.48; Н,
4.50; P, 8.17; S, 7.86. ESI-MS: m/z = 1529 [M+H]+ (calcd. М = 1528).
Calix[4]resorcinol 4a. The mixture of resorcinol (0.33 g, 3.00 mmol) and aldehyde 2
(0.82 g, 3.00 mmol) in ethanol (10 mL), water (10 mL), and concentrated hydrochloric acid
(5 mL) was stirred under heating at 70 ◦С for 3 days. The solvent was removed in vacuo
and the residue was dissolved in ethanol and reprecipitated in water. After drying (40 ◦С,
0.06 Torr), the product was obtained (0.94 g, 86%) as white powder. mp > 140 ◦С (dec.).
31Р NMR (166.93 MHz, acetone-d6): δ = 61.4 ppm. 1H NMR (600 MHz, acetone-d6): δ =
3
1.25 (t, JHH = 7.3 Hz, 24Н, CH3), 4.14 (m, 16Н, CH2), 5.75 (s, 2Н, H4h), 5.82 (s, 4H,
3
CH), 6.17 (s, 2Н, H4v), 6.21 (s, 2Н, H1v), 6.31 (s, 2Н, H1h), 6.53 (d, JHH = 7.6 Hz,
4Н, P O Car CHar CHar), 6.59 (s, 4Н, Car CHar Car), 6.83 (d, 3JHH = 8.0 Hz, 4H,
3
CH Car CHar CHar), 7.10 (t, JHH = 7.9 Hz, 4Н, P O Car CHar CHar), 7.34 (br.
m., 8Н, ОН) ppm. IR νmax: 820 (P S); 956, 1022 (P O C); 3100–3550 (ОН) cm−1
.
Anal. Calcd. for С68Н76O20P4S4: С, 55.74; Н, 5.19; P, 8.47; S, 8.74. Found: С, 55.22; Н,
5.38; P, 7.98; S, 8.77. ESI-MS: m/z = 1465 [M+H]+ (calcd. М = 1464).

CALIX[4]RESORCINOLS WITH THIOPHOSPHORYL-CONTAINING FRAGMENTS 1979
Calix[4]resorcinol 4b. This compound was obtained as white powder by a method
analogous to that used to prepare 4a by treatment of 2-methylresorcinol (0.38 g, 3.06
◦
mmol) with aldehyde 2 (0.84 g, 3.06 mmol). Yield 0.67 g (56%), mp > 250 С (dec.).
31Р NMR (166.93 MHz, DMSO-d6): δ = 61.4 ppm. H NMR (600 MHz, DMSO-d6):
1
δ = 1.22 (t, JHH = 7.0 Hz, 24H, CH3), 1.95 (s, 6H, H6h), 2.10 (s, 6H, H6v), 4.10 (m,
3
16H, CH2), 5.25 (s, 2Н, Н4h), 5.69 (s, 4H, CH), 6.14 (s, 2Н, Н4v), 6.42 (d, JHH
=
3
3
7.5 Hz, 4H, P O Car CHar CHar), 6.48 (s, 4H, Car CHar Car), 6.73 (d, JHH = 8.2
3
Hz, 4H, CH Car CHar CHar), 6.90 (t, JHH = 7.9 Hz, 4H, P O Car CHar CHar),
7.32 (s, 4H, OHv), 7.71 (s, 4H, OHh) ppm. IR νmax: 821 (P S); 953, 1022 (P O C);
3100–3600 (ОН) cm−1. Anal. Calcd. for С72Н84O20P4S4: С, 56.80; Н, 5.53; P, 8.16; S,
8.42. Found: С, 56.89; Н, 5.58; P, 8.33; S, 8.41. ESI-MS: 1521 [M+H]+ (calcd. М =
1520).
Calix[4]resorcinol 4c. This compound was obtained as dark pink powder by a method
analogous to that used to prepare 4a by treatment of pyrogallol (0.27 g, 2.14 mmol) with
aldehyde 2 (0.59 g, 2.14 mmol). Yield 0.53 g (65%), mp > 140 ◦С (dec.). 31Р NMR (166.93
MHz, acetone-d6): δ = 61.8 ppm. 1H NMR (600 MHz, acetone-d6): δ = 1.26 (m, 24Н, CH3),
4.15 (m, 16Н, CH2), 5.32 (s, 2Н, H4h), 5.84 (s, 4H, CH), 6.12 (s, 2Н, H4v), 6.61 (d, 3JHH
=
3
7.6 Hz, 4Н, P O Car CHar CHar), 6.65 (s, 4Н, Car CHar Car), 6.85 (d, JHH = 8.3
3
Hz, 4Н, CH Car CHar CHar), 7.00 (t, JHH = 7.93 Hz, 4Н, P O Car CHar CHar),
8.02 (br. m., 12Н, ОН) ppm. IR νmax: 819 (P S); 972, 1018 (P O C); 3100–3600
(ОН) cm−1. Anal. Calcd. for С68Н76O24P4S4: С, 53.40; Н, 4.97; P, 8.12; S, 8.38. Found:
C, 53.63; Н, 4.58; P, 8.04; S, 8.63. ESI-MS: 1529 [M+H]+ (calcd. М = 1528).
REFERENCES
1. G. A. Gainanova, E. P. Zhil’tsova, L. A. Kudryavtseva, S. S. Lukashenko, A. P. Timosheva, A.
R. Burilov, I. R. Knyazeva, and A. I. Konovalov, Russ. J. Gen. Chem., 76, 1788–1794 (2006).
2. A. Mustafina, J. Elistratova, A. Burilov, I. Knyazeva, R. Zairov, R. Amirov, S. Solovieva, and
A. Konovalov, Talanta, 68, 863–868 (2006).
3. T. N. Pashirova, S. S. Lukashenko, E. M. Kosacheva, M. V. Leonova, I. R. Knyazeva, A. R.
Burilov, L. A. Kudryavtseva, and A. I. Konovalov, Colloid J., 70, 202–209 (2008).
4. T. N. Pashirova, S. S. Lukashenko, E. M. Kosacheva, L. Z. Rizvanova, G. A. Gainanova, I. R.
Knyazeva, A. R. Burilov, L. A. Kudryavtseva, and A. I. Konovalov, Russ. Chem. Bull., Int. Ed.,
56, 959–966 (2007).
5. G. A. Gainanova, E. P. Zhiltsova, L. A. Kudryavtseva, S. S. Lukashenko, I. R. Knyazeva, A.
R. Burilov, V. I. Kovalenko, L. V. Avvakumova, and A. I. Konovalov, Russ. J. Gen. Chem., 77,
40–46 (2007).
6. L. M. Tunstad, J. A. Tucker, E. Dalcanale, J. Weiser, J. A. Bryant, J. C. Sherman, R. C. Helgeson,
C. B. Knobler, and D. J. Cram, J. Org. Chem., 54, 1305–1312 (1989).
7. E. U. Thoden van Velzen, J. F. Engbersen, and D. N. Reinhoudt, J. Am. Chem. Soc., 116,
3597–3598 (1994).
8. E. L. Gavrilova, A. A. Naumova, A. R. Burilov, M. A. Pudovik, E. A. Krasilnikova, and A. I.
Konovalov, Izv. Acad. Nauk SSSR, Seriya Khim. (Engl. Transl.), 11, 2269–2271 (2007).
9. E. L. Gavrilova, A. A. Naumova, N. I. Shatalova, A. R. Burilov, M. A. Pudovik, E. A. Krasil-
nikova, and A. I. Konovalov, Phosphorus Sulfur Silicon Relat. Elem., 183, 561–565 (2008).
10. N. M. Karayannis, C. M. Mikulski, and L. L. Pytlewski, Inorg. Chim. Acta Rev., 5, 69–105
(1971).
11. P. S. Pishchimuka, Zh. Russ. Fiz.-Khim. Obshch., Ser. Khim. (Russ. J. Phys. Chem. Soc., Ser.
Chem.), 44, 1406–1554 (1912).

1980
I. R. KNYAZEVA ET AL.
12. P. Delange, J.-C. Mulatier, B. Tinant, J.-P. Declercq, and J.-P. Dutasta, Eur. J. Org. Chem.,
3695–3704 (2001).
13. B. Bibal, B. Tinant, J.-P. Declercq, and J.-P. Dutasta, Supramol. Chem., 15, 25–32 (2003).
14. V. I. Maslennikova, O. S. Serkova, M. Gruner, S. Goutal, I. Bauer, W. D. Habicher, K. A.
Lyssenko, M. Yu. Antipin, and E. E. Nifantyev, Eur. J. Org. Chem., 4884–4893 (2004).
15. G. M. Sheldrick, SADABS, Program for Empirical X-ray Absorption Correction (Bruker-Nonius,
Go¨ttingen, Germany, 2004).
16. G. M. Sheldrick, SHELXTL v.6.12, Structure Determination Software Suite (Bruker AXS, Madi-
son, WI, 2000).
17. L. J. Farrugia, J. Appl. Crystalogr., 32, 837–838 (1999).
18. APEX2 (Version 2.1), SAINT Plus, Data Reduction and Correction Program (Version 7.31A)
(Bruker Advanced X-ray Solutions, Bruker AXS, Inc., Madison, WI, 2006).
19. A. L. Spek, J. Appl. Cryst., 36, 7–13 (2003).
20. G. M. Fazleeva, V. P. Gubskaya, F. G. Sibgatullina, V. V. Yanilkin, N. V. Nastapova, S. K.
Latypov, A. A. Balandina, I. E. Ismaev, V. V. Zverev, Y. Y. Efremov, and I. A. Nuretdinov, Izv.
Acad. Nauk SSSR, Seriya Khim. (Engl. Transl.), 3, 489–497 (2006).