Hydrogenation of α-oxophosphonates with molecular hydrogen catalyzed by palladium on carbon carrier as synthesis procedure for α- hydroxyphosphonates

Article abstract of DOI:10.1134/S1070428007080167

Hydrogenation with molecular hydrogen of substituted benzoylphosphonic acids ethyl esters provides a convenient preparation method for diethyl [hydroxy(aryl)methyl]phosphonates. Both the palladium on activated carbon and the palladium immobilized in a chitosan matrix applied on a carbon carrier sibunit can be employed as catalysts.

Full text of DOI:10.1134/S1070428007080167

ISSN 1070-4280, Russian Journal of Organic Chemistry, 2007, Vol. 43, No. 8, pp. 1180−1185. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © N.S. Gulyukina, G.N. Bondarenko, A.D. Averin, V.I. Isaeva, E.D. Finashina, L.M. Kustov, I.P. Beletskaya, 2007, published
in Zhurnal Organicheskoi Khimii, 2007, Vol. 43, No. 8, pp. 1186−1191.
Hydrogenation of α-Oxophosphonates with Molecular Hydrogen
Catalyzed by Palladium on Carbon Carrier as Synthesis Procedure
for α-Hydroxyphosphonates
N. S. Gulyukinaa, G. N. Bondarenkoa, A. D. Averina, V. I. Isaevab, E. D. Finashinab,
L. M. Kustovb, and I. P. Beletskayaa
aMoscow State University, Moscow, 119992 Russia
e-mail: goulioukina@org.chem.msu.ru
bZelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Moscow, Russia
Received February 7, 2007
Abstract—Hydrogenation with molecular hydrogen of substituted benzoylphosphonic acids ethyl esters provides
a convenient preparation method for diethyl [hydroxy(aryl)methyl]phosphonates. Both the palladium on activated
carbon and the palladium immobilized in a chitosan matrix applied on a carbon carrier sibunit can be employed
as catalysts.
DOI: 10.1134/S1070428007080167
(only unsuccessful attempt on hydrogenation in the
presence of Raney nickel was mentioned [16]). Presum-
ably this gap is due to the lability of the α-oxophos-
phonates in the presence of transition metal complexes
[17] and also to the ready rupture of the P–C bond of the
α-hydroxyphosphonates through a retro-Abramov
reaction or a phosphonate-phosphate rearrangement (see,
e.g., [16, 18, 19]). Whereas the hydrogenation of β-oxo-
phosphonates was well known and was used, in
particular, in the preparation of optically active
β-hydroxyphosphonates [20–22], to the synthesis of the
α-hydroxyphosphonates the hydrogenation with
molecular hydrogen was applied only in the case of
prochiral α,β-unsaturated precursors, 1-benzoyloxy-
alkenylphosphonates (O-benzoylated enol form) [23–25].
We believed that it was interesting to estimate the pos-
sibility to subject the α-oxophosphonates to the hydro-
genation with molecular hydrogen; a commercially avail-
able palladium on carbon and also a palladium immobiliz-
ed on chitosan matrix applied on a carbon carrier sibunit
were chosen for catalysts.
α-Hydroxyphosphonates are extensively studied first
of all due to their probable application as drugs and
bioregulators [1]. The basic synthetic procedures for
α-hydroxyphosphonates are the hydrophosphonylation
of carbonyl compounds (Abramov reaction) [2] and the
reduction of available α-oxophosphonates [3]. The reduc-
tion of diethyl α-benzoylphosphonate in [4] was perform-
ed with sodium amalgam in aqueous-alcoholic solution
of acetic acid. Further mostly boron hydrides were used
as reductants: lithium triethylborodeuteride [5], and
sodium borohydride [6–10]. At the use of a complex of
NaBH4 with L-(+)-tartaric acid [11] or of an optically
active chloroborane containing pinane residue [12] the
reduction the α-oxophosphonates occurred stereoselec-
tively. An asymmetric catalytic reduction was achieved
with the help of catecholborane in the presence of (S)-2-
butyl-5,5-diphenyl-3,4-propano-1,3,2-oxazaborolidine
[13–15].
No published data existed on the catalytic hydro-
genation of α-oxophosphonates with molecular hydrogen
O
OH
R
R
H2, Pd-catalyst (5 mol%)
P(O)(OEt)2
P(O)(OEt)2
Ia_Id
IIa_IId
R = H (a), 4-Me (b), 2-Me (c), 4-MeO (d).
1180

HYDROGENATION OF α-OXOPHOSPHONATES
1181
Hydrogenation of diethyl aroylphosphonates with hydrogen in the presence of palladium catalysts
Run
Initial
Pressure, Temperature, Reaction Conversion,
Yield of
compound II, %
Pd-catalyst
10%Pd/C
Solvent
no. compound
at
1
1
1
1
1
°C
65
20
65
65
65
20
78
78
78
78
78
20
time, h
%
100
92
1
2
Ia
Ia
Ib
Id
Iс
Iс
Ia
Ia
Ib
Id
Iс
Iс
MeOH
MeOH
MeOH
MeOH
MeOH
MeOH
EtOH
1.5
1
96
81
99
95
7
10%Pd/C
3
10%Pd/C
2
100
100
55
4
10%Pd/C
1
5
10%Pd/C
1
6
10%Pd/C
10
6
100
100
85
100
89
57
78
72
53
72
7
1%Pd/chitosan/sibunit
3%Pd/chitosan/sibunit
1%Pd/chitosan/sibunit
1%Pd/chitosan/sibunit
1%Pd/chitosan/sibunit
1%Pd/chitosan/sibunit
1
1
3
8
EtOH
3
9
EtOH
1
3
90
10
11
12
EtOH
1
3
75
EtOH
1
3
62
MεOH
10
6
81
We selected for model compounds diethyl esters of
benzoylphosphonic acids substituted in the ring Ia–Id
and diethyl acetylphosphonate (Ie). The reactions were
carried out in methanol or ethanol at the hydrogen
pressure 1 at. The reaction progress was monitored by
31P{H} NMR following the disappearance of the signal
of the initial α-oxophosphonate I at δ –2.7÷–0.5 ppm
and the accumulation of the signal of α-hydroxy-
phosphonate II at δ 21.8–22.5 ppm. The results obtained
presented in the table show that in the presence of
5 mol% of 10% Pd on carbon diethyl benzoylphos-
phonate (Ia) is easily hydrogenated with hydrogen in
the boiling methanol: at 100% conversion the yield of
diethyl [hydroxy(phenyl)methyl]phosphonate (IIa)
reaches 96% in 1.5 h (run no. 1). In the reaction at the
room temperature the conversion within 1 h was 92%,
but the selectivity of the process considerably reduced,
and the yield of the target product was but 81% (run
no. 2).
reaction products appeared diethyl (19%), dimethyl (5%),
and mixed (3%) phosphites (run no. 5). Nearly the same
results were obtained on replacing methanol by higher
boiling ethanol. We succeeded to obtain α-hydroxy-
phosphonate IIc in quantitative yield by increasing the
hydrogen pressure to 10 at (run no. 6). We believe that
the considerable decrease in selectivity at the hydro-
genation of α-oxophosphonate Ic on 10%Pd/C at the
atmospheric pressure is caused by diffusion limitations
which are removed in the reaction carried out at higher
pressure.
The hydrogenation rate at the use of palladium catalyst
based on chitosan applied on sibunit (Pd/chitosan/sibunit)
proved to be somewhat lower that that for 10%Pd/C (cf.
runs nos. 1 and 7). At the palladium content in the sample
of 1 wt% the quantitative conversion of α-oxophos-
phonate Ia in the presence of 5 mol% of 1%Pd/chitosan/
sibunit was reached within 3 h in boiling ethanol;
therewith the yield of the target product IIa was 89%
(run no. 7). The replacement of methanol by ethanol in
this case was due to low reproducibility of results
obtained in MeOH (by yet unknown reasons).
Introduction of donor substituents into the aromatic
ring of benzoylphosphonate is known [18] to decrease
its tendency to reduction; however, in the presence of
10%Pd/C substrates Ib and Id containing methyl and
methoxy substituents in the para-position are hydro-
genated as readily as Ia giving the corresponding α-hy-
droxyphosphonates IIa and IIb in nearly quantitative
yield (runs nos. 3 and 4).
The increase in the palladium concentration on the
carrier from 1 to 3 wt% resulted in considerable reduction
in the catalyst activity: under the same conditions the
conversion and yield diminished to 85 and 57% respec-
tively (run no. 8). The investigation of the samples of
Pd/chitosan/sibunit by scanning electron microscopy
revealed (see the figure) that unlike the systems based
on silica gel [26] the chitosan unevenly covered the
sibunit surface. It is presumably caused by the hydro-
phobicity of the surface of sibunit that is a carbon carrier,
We met difficulties in hydrogenation of the sterically
hindered substrate Ic containing an ortho-methyl
substitutent. In boiling methanol the conversion of
compound Ic within 1 h attained 55%, and the yield of
α-hydroxyphosphonate IIc, 7%; among the other
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

GULYUKINA et al.
1182
whereas the silica gel is hydrophilic. 2000-Fold
magnification clearly shows that the polymer coats
the sibunit surface unevenly, with cracks, and this fact
is especially obvious for the sample containing 3 wt%
of palladium and consequently larger amount of
the polymer. In this catalyst at 5000-fold magnifica-
tion separate isles of palladium/chitosan complex are
visible. We presume that this nonuniformity results in
formation of at least two types of catalytic centers:
heterogeneous, namely, Pd on sibunit, and heterogenized,
Pd immobilized in a chitosan matrix applied on sibunit
surface.
In the presence of 1%Pd/chitosan/sibunit the
decelerating effect of electon-donor groups is revealed:
the hydrogenation rate of α-oxophosphonate Ib (see the
table, run no. 9) and especially Id (run no. 10) are
Results of investigation of surface of sibunit and samples Pd/chitosan/sibunit with alternating palladium content by scanning
electron microscopy
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

HYDROGENATION OF α-OXOPHOSPHONATES
1183
1
considerably reduced, although the selectivity of the
process is not notably affected. In contrast, the sterical
factor at the use of 1%Pd/chitosan/sibunit is not so
important as with 10%Pd/C. The hydrogenation rate in
going from 4-methyl-substituted α-oxophosphonate Ib
(run no. 9) to 2-methyl-substituted α-oxophosphonate
Ic (run no. 11) decreases, but not as significantly as at
the use of palladium on carbon (cf. runs nos. 3 and 5).
Presumably the observed reduced sensitivity to the steric
factor in the system 1%Pd/chitosan/sibunit is due to the
above mentioned presence on the catalyst surface of two
types of active centers. Probably in the hydrogenation
reaction on the second type heterogenized centers the
diffusion limitations are not as severe as in the system
10%Pd/C.
from an external reference 85% H3PO4, in H NMR
spectra, from internal reference TMS, and in 13C NMR
spectra, from the solvent signal (CDCl3 77.0 ppm,
CD3OD 49.0 ppm). The microphoto of catalyst samples
were obtained using scanning microscope JSM-5300LV
JEOL. A thin layer of gold was applied on the sample
surface on a JFC-1100E instrument. Methanol and
ethanol were boiled and distilled over magnesium
methylate and calcium ethylate respectively. Palladium
on carbon (10%Pd/C) was purchased from Aldrich.
1%Pd/chitosan/sibunit. Sibunit (7 g, fraction 0.63–
1.00 mm, SBET 300 m2/g, moisture capacity 1.0 ml/g)
was impregnated with 7.0 ml of chitosan solution in 1%
aqueous acetic acid (chitosan content in the solution
8 g/l). After drying in air the sibunit sample coated with
chitosan was treated with 0.105 ml of 50% water solution
of glutaric aldehyde in 20 ml of MeOH for 1 h (calculated
degree of crosslinking 10%). Then the sample was
washed with MeOH and dried in air. The treatment of
sibunit with chitosan and glutaric aldehyde was
performed three times in succession. Thus prepared
system chitosan/sibunit was treated with a solution of
0.194 g of Na2PdCl4 in 15 ml of H2O. Palladium-
containing sample was washed with water and MeOH,
dried in air, and then in a vacuum-desiccator over P2O5.
Our attempt to replace the carbon carriers by silica
gel failed. We formerly demonstrated [26] that a three-
component palladium-containing system based on
chitosan applied on silica gel and modified with glutaric
aldehyde exhibited a high catalytic activity in hydro-
genation (also chemoselective) of α,β-unsaturated phos-
phonic acids and their esters. With α-oxophosphonate
Ia the application of this catalyst resulted in decomposi-
tion with the formation of diethyl phosphite.
Unlike aromatic α-oxophosphonates Ia–Id aliphatic
diethyl acetylphosphonate (Ie) did not undergo hydro-
genation in the boiling methanol either in the presence
of the palladium on carbon or on sibunit; the main
reaction product was diethyl phosphite containing a small
amount of dimethyl and methylethyl phosphates. The
formation of diethyl (1-hydroxyethyl)phosphonate (IIe)
was detected only in reaction performed at room tempera-
ture; in the presence of 10%Pd/C at 75% conversion of
compound Ie after 1 h the yield of compound IIe was
11%, that of diethyl phosphite 64%.
Thus we demonstrated that unlike aliphatic α-oxo-
phosphonates the hydrogenation of benzoylphosphonic
acids esters can be a convenient method of preparation
of [hydroxy(aryl)methyl]-phosphonates. As the hydro-
genation catalyst may be used both palladium on the
activated carbon and that immobilized in a chitosan
matrix applied on carbon carrier sibunit.
3%Pd/chitosan/sibunit was prepared in a similar
way. The treatment of sibunit with chitosan and glutaric
aldehyde was performed nine times in succession.
Palladium was applied from a solution of 0.582 g of
Na2PdCl4 in 20 ml of H2O.
α-Oxophosphonates Ia–Ie were prepared by
standard procedures [4, 27–29] and purified by
distillation; their spectral characteristics are given below.
Diethyl benzoylphosphonate (Ia) [4, 27], bp. 145°C
1
(2 mm Hg). H NMR spectrum (CDCl3), δ, ppm:
3
1.39 d.t (6H, CH3, JHH 7.1, 4JPH 0.5 Hz), 4.29 m (4H,
3
4
CH2), 7.52 m (2Harom), 7.64 t.t (1Harom, JHH 7.5, JHH
1.3 Hz), 8.28 m (2Harom). 31P{H} NMR spectrum
(CDCl3), δ, ppm: –1.1.
Diethyl (4-methylbenzoyl)phosphonate (Ib), bp
155°C (2 mm Hg). 1H NMR spectrum (CDCl3), δ, ppm:
1.38 t (6H, CH3CH2, 3JHH 7.2 Hz), 2.42 s (3H, CH3Ph),
4.28 m (4H, CH2), 7.31 d (2Harom, 3JHH 7.9 Hz), 8.18 d
3
(2Harom, JHH 7.9 Hz). 13C NMR spectrum (CDCl3),
EXPERIMENTAL
3
δ, ppm: 16.26 (CH3, JPC 5.9 Hz), 63.93 (CH2,
2JPC 7.6 Hz), 128.75 (2CHarom), 129.73 (2CHarom), 134.67
(CHarom), 135.44 (Carom, 2JPC 64.1 Hz), 198.86 (CO,
1JPC 175.4 Hz). 31P{H} NMR spectrum (CDCl3), δ, ppm:
–0.9.
1H, 13C, and 31P{H} NMR spectra were registered on
a spectrometer Bruker Avance-400 at operating
frequencies 400, 101, and 162 MHz respectively. The
chemical shifts were measured in 31P{H} NMR spectra
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

GULYUKINA et al.
1184
Diethyl (2-methylbenzoyl)phosphonate (Ic), bp
(CH2, 2JPC 8.1 Hz), 71.44 (CHP, 1JPC 166.1 Hz), 128.58
(2CHarom, JPC 5.1 Hz), 129.10 (CHarom), 129.15
(2CHarom), 138.70 (Carom). 31P NMR spectrum (CD3OD),
3
126–130°C (1 mm Hg). 1H NMR spectrum (CDCl3), δ,
3
ppm: 1.37 t (6H, CH3CH2, JHH 7.1 Hz), 2.54 s
(3H, CH3Ph), 4.27 m (4H, CH2), 7.28 d (1Harom
,
δ, ppm: 21.8.
3JHH 7.2 Hz), 7.35 t (1Harom), 7.46 t (1Harom), 8.46 d
Compounds IIb and IId were similarly obtained.
3
13
(1Harom, JHH 7.8 Hz). C NMR spectrum (CDCl3), δ,
ppm: 16.13 (CH3CH2, 3JPC 5.1 Hz), 21.62 (CH3Ph), 63.61
(CH2, 2JPC 7.3 Hz), 129.34 (2CHarom), 129.75 (2CHarom),
133.16 (Carom, 2JPC 64.4 Hz), 145.79 (Carom), 198.07 (CO,
1JPC 173.8 Hz). 31P{H} NMR spectrum (CDCl3), δ, ppm:
–1.2.
Diethyl [hydroxy(4-methylphenyl)methyl]phos-
phonate (IIb). Yield 99%. 1H NMR spectrum (CDCl3),
δ, ppm: 1.20 t (3H, CH3CH2, 3JHH 7.1 Hz), 1.26 t (3H,
3
CH3CH2, JHH 7.0 Hz), 2.34 s (3H, CH3Ph), 3.94–
2
4.08 m (4H, CH2), 4.96 d (1H, CHP, JHP 10.6 Hz),
7.15 d (2Harom, 2JHH 7.8 Hz), 7.36 d.d (2Harom, 2JHH 7.8,
4JPH 1.5 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 16.27
Diethyl (4-methoxybenzoyl)phosphonate (Id) [27,
1
28]. H NMR spectrum (CDCl3), δ, ppm: 1.38 t (6H,
3
3
(CH3CH2, JPC 3.6 Hz), 16.32 (CH3CH2, JPC 5.0 Hz),
CH3CH2, 3JHH 7.1 Hz), 3.89 s (3H, CH3O), 4.27 m (4H,
CH2), 6.98 d (2Harom, 3JHH 8.8 Hz), 8.29 d (2Harom, 3JHH
8.8 Hz). 13C NMR spectrum (CDCl)3, δ, ppm: 16.16
2
21.09 (CH3Ph), 62.93 (CH2, JPC 7.2 Hz), 63.18 (CH2,
2JPC 7.2 Hz), 70.63 (CHP, JPC 160.3 Hz), 127.02
1
(2CHarom, 3JPC 5.9 Hz), 128.88 (2CHarom), 133.64 (Carom),
137.68 (Carom). 31P NMR spectrum (CDCl3), δ, ppm: 22.0.
3
(CH3CH2, JPC 5.9 Hz), 55.42 (CH3O), 63.62 (CH2,
2JPC 6.7 Hz), 63.22 (CH2, 2JPC 6.7 Hz), 113.95 (2CHarom),
128.78 (Carom, 2JPC 64.9 Hz), 132.29 (2CHarom), 164.73
Diethyl hydroxy(4-methoxyphenyl)methyl]phos-
phonate (IId) [30, 31]. Yield 95%. 1H NMR spectrum
(CDCl3), δ, ppm: 1.21 t (3H, CH3CH2, JHH 7.1 Hz),
1.27 t (3H, CH3CH2, JHH 7.1 Hz), 3.8 s (3H, CH3O),
1
(Carom), 196.34 (CO, JPC 173.7 Hz). 31P{H} NMR
3
spectrum (CDCl3), δ, ppm: –0.5.
3
Diethyl acetylphosphonate (Ie) [29], bp. 96–99°C
(12 mm Hg). 1H NMR spectrum (CDCl3), δ, ppm: 1.39 t
3.91–4.09 m (4H, CH2), 4.95 d (1H, CHP, 2JHP 10.1 Hz),
6.88 d (2Harom, 2JHH 8.7 Hz), 7.41 d.d (2Harom, 2JHH 8.7,
4JPH 1.5 Hz). 13C NMR spectrum (CDCl3), δ, ppm: 16.32
(CH3CH2), 55.16 (CH3O), 62.91 (CH2, 2JPC 7.6 Hz) 63.22
(CH2, 2JPC 6.7 Hz), 70.23 (CHP, 1JPC 161.0 Hz), 113.61
(2CHarom), 128.41 (2CHarom, 3JPC 6.8 Hz), 128.67 (Carom),
159.37 (Carom). 31P NMR spectrum (CDCl3), δ, ppm: 22.1.
Diethyl hydroxy(2-methylphenyl)methyl]phos-
phonate (IIc). Into a steel pressure reactor with a glass
lining equipped with a magnetic stirrer and flushed with
dry argon was charged 0.056 g (0.2 mmol) of α-oxo-
phosphonate Ic in 4 ml of anhydrous methanol and
0.011 g (5 mol%) of 10%Pd/C. The hydrogen pressure
was raised to 10 at, and the reaction mixture was stirred
at room temperature for 6 h. The catalyst was filtered
off through a thin bed of silica gel, and the solvent was
distilled off on a rotary evaporator. The residue was
dissolved in CDCl3and subjected to spectral analyses.
Yield according to the data of 31P{H} NMR spectrum
was 100%. 1H NMR spectrum (CDCl3), δ, ppm: 1.20 t
(3H, CH3CH2, 3JHH 7.0 Hz), 1.26 t (3H, CH3CH2, 3JHH
7.0 Hz), 2.37 s (3H, CH3Ph), 3.90–4.10 m (4H, CH2),
3
(6H, CH3CH2, JHH 7.1 Hz), 2.49 d (3H, CH3CO,
3JPH 5.2 Hz), 4.21 m (4H, CH2). 31P{H} NMR spectrum
(CDCl3), δ, ppm: –2.7.
Diethyl [hydroxy(phenyl)methyl]phosphonate
(IIa) [4, 5, 13, 30]. Into a flask equipped with a magnetic
stirrer, a reflux condenser with a Wuertz adapter, a long
capillary going through the condenser to the bottom of
the flask, and a bubbler was charged 0.05 g (0.2 mmol)
of compound Ia in 4 ml of anhydrous methanol. The
device was filled with argon through the capillary, and
0.01 g (5 mol%) of 10%Pd/C was charged thereto. The
argon flow was stopped, and through the same capillary
the device was flushed with hydrogen. The reaction
mixture was heated at reflux for 1 h under a constant
flow of hydrogen while stirring, then it was cooled, the
catalyst was filtered off through a thin bed of silica gel,
and the solvent was distilled off on a rotary evaporator.
The residue was dissolved in CD3OD and subjected to
spectral analyses. Yield according to the data of 31P{H}
NMR spectrum was 96%. 1H NMR spectrum (CD3OD),
δ, ppm: 1.22 t (3H, CH3, 3JHH 7.1 Hz), 1.26 d.t (3H, CH3,
2
4.50 br.s (1H, OH), 5.27 d (1H, CHP, JHP 10.9 Hz),
4
3JHH 7.1, JPH 0.5 Hz), 3.95–4.10 m (4H, CH2), 4.80 s
7.14 d (1Harom
,
3JHH 7.1 Hz), 7.22 m (2Harom), 7.66 d
2
3
(1Harom, JHH 7.3 Hz). 13C NMR spectrum (CDCl3), δ,
ppm: 16.26 (CH3CH2, 3JPC 4.4 Hz), 16.31 (CH3CH2,3JPC
5.1 Hz), 19.48 (CH3Ph), 62.88 (CH2, 2JPC 7.3 Hz), 63.36
(CH2, 2JPC 7.3 Hz), 67.02 (CHP, 1JPC 160.3 Hz), 126.01,
(1H, OH), 5.00 d (1H, CHP, JHP 12.9 Hz), 7.29 m
(1Harom), 7.35 m (2Harom), 7.48 m (2Harom). 13C NMR
3
spectrum (CD3OD), δ, ppm: 16.66 (CH3, JPC 5.9 Hz),
16.72 (CH3, 3JPC 5.9 Hz), 64.24 (CH2, 2JPC 7.3 Hz), 64.55
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 43 No. 8 2007

HYDROGENATION OF α-OXOPHOSPHONATES
1185
127.16, 127.85, 130.09 (CHarom), 135.10 (Carom), 135.67
(Carom, 2JPC 6.6 Hz). 31P NMR spectrum (CDCl3), δ, ppm:
22.5.
ti, P., Pollini, G.P., and Zanirato, V., Tetrahedron Lett., 1999,
vol. 40, p. 7705.
16. Horner, L. and Roder, H., Chem. Ber., 1970, vol. 103,
p. 2984.
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The study was carried out under a financial support of the
Russian Foundation for Basic Research (grants nos. 05-03-
33013 and 04-03-39017-GFEN) and INTAS (grant no.05-
1000008-80614).
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