Synthesis of β-carbonylphosphine oxides and phenyl-substituted ethylenediphosphine oxides. study of their complexing with alkali metals cations

Article abstract of DOI:10.1134/S1070363209100065

The synthesis of some β-carbonylphosphine oxides and phenyl-substituted ethylenediphosphine oxides was carried out. Their complexing with alkali metals cations was studied. Compounds obtained were shown to possess clearly expressed Li/Na selectivity.

Full text of DOI:10.1134/S1070363209100065

ISSN 1070-3632, Russian Journal of General Chemistry, 2009, Vol. 79, No. 10, pp. 2113–2115. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.E. Antoshin, Yu.N. Reikhov, K.V. Tugushov, I.V. Rybal’chenko, V.F. Taranchenko, S.A. Lermontov, A.N. Malkova, 2009,
published in Zhurnal Obshchei Khimii, 2009, Vol. 79, No. 10, pp. 1618–1620.
Synthesis of β-Carbonylphosphine Oxides
and Phenyl-Substituted Ethylenediphosphine Oxides.
Study of Their Complexing with Alkali Metals Cations
A. E. Antoshina, Yu. N. Reikhova, K. V. Tugushova, I. V. Rybal’chenkob,
V. F. Taranchenkob, S. A. Lermontovc, and A. N. Malkovac
a Civil Defence Academy, Ministry of the Emergency Situations, Khimki, Moscow, Russia
b Federal State Institution “27 Scientific Centre of Defence Ministry of the Russian Federation,” Moscow, Russia
c Institute of Physiologically Active Compounds, Russian Academy of Sciences
Severnyi proyezd, 1, Chernogolovka, Moscow oblast, 142432 Russia
e-mail: lermon@ipac.ac.ru
Received April 9, 2009
Abstract―The synthesis of some β-carbonylphosphine oxides and phenyl-substituted ethylenediphosphine
oxides was carried out. Their complexing with alkali metals cations was studied. Compounds obtained were
shown to possess clearly expressed Li/Na selectivity.
DOI: 10.1134/S1070363209100065
We reported earlier on developing chemical
methods to utilize toxic organoelemental compounds,
including sulfur and cyano-containing [1] and
organochlorine pesticides [2]. To continue these works
we studied the development of chloro-acetophenone
(CAP) utilization methods. Great amount of this
substance were stored on the chemical arsenals, during
which the warranty period of its storage expired.
The considerably low yield of compound II in
comparison with analogs has engaged our attention.
Evidently, this fact was due to high losses on the
isolation stage.
All of the compounds obtained are well soluble in
aromatic hydrocarbons (benzene, toluene) and non-polar
organic solvents. It should be pointed out especially
that compound II is soluble at room temperature in
hydrocarbons of normal structure up to n-pentane.
For this purpose we studied reaction of CAP with
hydrophosphoryl compounds [phosphinous acids
R2P(O)H]. The reaction was not examined earlier. We
presumed that some substituted β-carbonylphosphine
oxides might be obtained. These compounds contain-
ing two donor centers are of interest as potential
bidentate ligands and extracting agents.
We synthesized series of phenyl-substituted ethylene-
diphosphine oxides unreported earlier to obtain
comparative characteristics of ligand possibility of the
new prepared β-carbonylphosphine oxides against the
others bidentate ligands and extracting agents. The
choice of the phenyl group as a substituent in the
ethylene bridge was done to increase the diphosphine
oxides solubility in non-polar and aromatic solvents.
We found that reaction of chloroacetophenone with
phosphinous acids proceeds by the following scheme:
2 R2P(O)H + C6H5CHClCH2Cl + 2 NaOH
PhC(O)CH2Cl + R2P(O)
DMSO
KOH
R2P1(O)CH2CH[P2(O)R2]C6H5 + 2 NaCl + 2 H2O.
(DMF)
PhC(O)CH2P(O)R2 + KCl + H2O.
I–V
VI–IX
Yields, some constants, and NMR spectra param-
eters for phenyl-substituted ethylenephosphine oxides
are given in Tables 2, 3.
Reaction was carried out under mild conditions
using DMSO or DMFA as solvents at 60–65°С for
1.5–2 h. Yields and some constants are given in Table 1.
2113

2114
ANTOSHIN et al.
Table 1. Yields, melting points, elemental analysis data and NMR spectra parameters for β-carbonylphosphine oxides
Found, %
H
Calculated, %
H
Comp.
no.
Yield,
%
δР,
R
mp, оС
Formula
ppm
C
P
C
P
C2H5
68
41
118–120
64.31
8.01
14.01
7.67
C12H17O2P
C24H41O2P
64.27
7.64
13.81
7.88
31.3
29.4
I
n-C8H17
–
73.80 10.29
73.43 10.53
II
(bp 220–228/10–4 mm)
C6H5
78
81
73
212–214
159–161
–
75.30
76.13
77.01
5.19
6.11
5.58
9.41
9.13
9.38
C20H17O2P
C22H21O2P
C22H21O2P
74.99
75.91
75.91
5.34
6.08
6.08
9.67
8.90
8.90
30.6
33.2
37.1
III
IV
V
C6H5CH2
п-CH3C6H4
а
a In this work technical ditolylphosphinous acid was used (by NMR spectrum data, 90–94%).
Table 2. Yields, melting points and elemental analysis data for phenyl-substituted ethylenediphosphine oxides
Found, %
H
Calculated, %
Comp.
no.
R
Yield, %
mp, оС
Formula
C
P
C
H
P
C2H5
54
32
88
82
106–109
61.09
73.19
75.78
77.12
8.67
19.56
10.20
12.27
11.35
C16H28O2P2
C38H76O2P2
C32H28O2P2
C36H36O2P2
61.13
72.80
75.88
76.85
8.98
12.22
5.57
6.45
19.71
9.88
VI
n-C8H17
C6H5
–
192–194
–
12.41
5.81
VII
VIII
IX
12.23
11.01
C6H5CH2
6.62
As follows from Table 2, the target products yields
are sufficiently high except for compound VII. This
fact may also originate from high losses on the
isolation stage.
Properties of compounds obtained were evaluated
by stability constant values of their complexes with
alkali metals cations of the corresponding 2,4-
dinitrophenolates. The ratio of stability constants
values of lithium and sodium complexes was used for
selectivity estimating. Data about complexing ability
and selectivity are given in Table 4.
As early as the nineteen seventies phosphine oxides
and alkylenediphosphine oxides were established to
form complex compounds of various stability with
metal cations [3]. Various methods for quantitative
estimation of the ligand properties of alkylenedi-
phosphonates with respect to metal cations were used,
but electroconductivity measurement method was the
most common [4].
As follows from these data, all of the compounds
obtained are effective ligands for alkali metals cations.
Compound III is of greater practical interest since it
combined the sufficiently high absolute value log β
with high Li/Na-selectivity close to the most effective
from the known [5] organophosphorus compounds.
EXPERIMENTAL
Table 3. NMR spectra parameters for phenyl-substituted
ethylenediphosphine oxides
All the reactions involving phosphonous acids were
carried out under a dry argon atmosphere. Purification
and individuality of compounds obtained were
monitored by TLC on Silufol UV-254 plates eluting
with systems chloroform-acetone (1:1) and
chloroform–ethanol (20:1). Melting points were
determined on a Boetius PHMK-05 device. The 31P
NMR spectra were registered on a spectrometer Bruker
Comp.
δ(Р1), ppm
δ(Р2), ppm.
J (P1P2), Hz
no.
29.1
32.0
27.1
29.9
56.9
52.8
54.5
38.1
44.0
44.2
44.6
48.6
VI
VII
VIII
IX
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 10 2009

SYNTHESIS OF β-CARBONYLPHOSPHINE OXIDES
2115
Table 4. Logarithms of stability constants (log β) for com-
plexes M+L with alkali metals cations in the mixture THF–
CHCl3 4:1 at 25°С
of 45% of potassium hydroxide solution. The reaction
mixture was stirred for 2 h, then cooled, diluted with
water (70 ml), and extracted with chloroform (370 ml).
Organic layer was separated, washed with water (4×
50 ml), and dried with MgSO4. Solvent was removed
in a vacuum. Yield 12.5 g (78%), after recrystal-
lization from dioxane, 11.5 g (72%).
log β
Selectivity
Comp. no.
Β(Li)/β(Na)
Li
Na
2.6
3.4
3.7
4.6
3.3
3.1
3.0
3.6
4.2
6.3
6.3
35
I
2.9
3.0
2.8
2.2
2.0
2.9
3.1
II
Diphosphine oxide (VIII) was prepared similarly
from 10.5 g of diphenylphosphinous acid, 8.7 g
(6.9 ml) of 1-phenyl-1b,-dichloroethane and 9.0 ml of
45% potassium hydroxide solution (10% excess).
Yield 25.3 g (88%), after recrystallization from dioxane,
17.7 g (69%).
III
IV
V
3.2
7.9
10
VI
VII
VIII
5.0
12.5
REFERENCES
1. Antoshin, A.E., Lermontov, S.A., Reikhov, Yu.N.,
Tugushov, V.I., and Tugushov, K.V., Khim. i Biol.
Bezop., 2006, no. 6 (30), p. 10.
2. Antoshin, A.E., Lermontov, S.A., Reikhov, Yu.N., and
Tugushov, K.V., Khim. i Biol. Bezop., 2008, nos. 1–2
(37–38), p. 12.
CXP-200 relative to external 85% H3PO4 using CDCl3
as a solvent. The downfield chemical shifts were
considered to be positive. Quantitative estimation of
ligand ability (L) was made using stability constants
values [M+]L measured by conductometric method.
Procedure of these measurements performed at 25°С in
THF–CHCl3 (4:1) system is described in [4]. Precision
error < 0.1 log units. Alkali metals 2,4-dinitro-
phenolates were used as salts.
3. Medved’, T.Ya., Polikarpov, Yu.M., Bertina, L.E., and
Kabachnik, M.I., Usp. Khim., 1975, no. 6, p. 1003.
4. Yatsimirskii, K.B., Kabachnik, M.I., Medved’, T.Ya.,
and Sinyavskaya, E.I., Izv. Akad. Nauk SSSR Ser. Khim.,
1988, no. 1, p. 58.
Phosphine oxide (III). To a solution of 10.5 g of
diphenylphosphonous acid and 7.7 g of chloroaceto-
phenone in 70 ml of DMSO at 60°С was added 4.3 ml
5. Yevreinov, V.I., Vostroknutova, Z.N., Baulin, V.E.,
Syundyukova, V.Kh., and Tsvetkov, E.N., Zh. Obshch.
Khim., 1989, vol. 59, no. 1, p. 79.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 79 No. 10 2009