Synthesis and extractive properties of dialkylaminomethyl-substituted dialkylamides of diphenylphosphinoylacetic acid

Article abstract of DOI:10.1007/s11176-005-0366-z

Dialkylamides of diphenylphosphinoylacetic acids, dialkylaminomethyl-substituted by the methylene group, were prepared by means of the Mannich reaction from diphenyl(dialkylcarbamoylmethyl)-phosphine oxides or by reaction of the latter compounds with tetr

Full text of DOI:10.1007/s11176-005-0366-z

Russian Journal of General Chemistry, Vol. 75, No. 7, 2005, pp. 1050 1056. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 7, 2005,
pp. 1111 1117.
Original Russian Text Copyright
2005 by Yarkevich, Turanov, Kharitonov.
Synthesis and Extractive Properties
of Dialkylaminomethyl-substituted Dialkylamides
of Diphenylphosphinoylacetic Acid
A. N. Yarkevich*, A. N. Turanov**, and A. V. Kharitonov*
* Institute of Physiologically Active Substances, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
** Institute of Solid State Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Received October 21, 2003
Abstract Dialkylamides of diphenylphosphinoylacetic acids, dialkylaminomethyl-substituted by the
methylene group, were prepared by means of the Mannich reaction from diphenyl(dialkylcarbamoylmethyl)-
phosphine oxides or by reaction of the latter compounds with tetraethylmethylenediamine. Extractive ability
of the obtained compounds toward U(VI) and Pd(II) in nitrate media was studied.
Alkylation of dialkylamides of diphenylphosphi-
noylacetic acid by the methylene group is most com-
monly complicated by the low CH acidity of me-
thylene protons. For this reason, -alkyl-substituted
dialkylamides of diphenylphosphinoylacetic acid are
usually prepared starting from potassium derivatives
of corresponding dialkylamides [1] or preliminary
synthesized -alkyl-substituted diphenylphosphinoyl-
acetic acids [2]. In the present work we studied feasi-
bility of direct dialkylaminomethylation of certain
dialkylamides of diphenylphosphinoylacetic acid for
preparing complex-forming agents of a new type.
Ethyl (diethoxyphosphinoyl)acetate whose methy-
lene protons exhibit enhanced acidity due to the elec-
tron-acceptor effect of the ethoxycarbonyl group
reacts with Formalin and diethylamine under Mannich
reaction conditions to form a condensation product,
diethyl 2,4-bis(diethoxyphosphinoyl)pentane-1,5-dioic
acid [3].
(EtO)2P(O)CHC(O)OEt
CH2
(EtO)2P(O)CH2C(O)OEt + Et2NH + CH2O
(EtO)2P(O)CHC(O)OEt
Unlike ethyl (diethoxyphosphinoyl)acetate, N,N-di-
alkyl(diphenylphosphinoyl)acetamides Ph2P(O)CH2
C(O)NR2 Ia Ic [R = Et (a), i-Bu (b), Hex (c)] form
under analogous conditions -dialkylaminomethyl-
substituted derivatives that combine three types of
complex-forming groups in one molecule and, there-
fore, are perspective to study as extractants.
Amides Ia and Ib can be converted to dialkyl-
aminomethyl derivatives IIIa IIIc under usual
Mannich reaction conditions, i.e. by the reaction with
equimolar amounts of formaldehyde and dialkylamine
at 60 80 C (method a).
(a)
Ph2P(O)CH2C(O)NR2 + R2NH + CH2O
Ph2P(O)CHC(O)NR2
CH2NR2
IIIa IIIc
Ia, Ib
IIa, IIb
1070-3632/05/7507-1050 2005 Pleiades Publishing, Inc.

SYNTHESIS AND EXTRACTIVE PROPERTIES OF DIALKYLAMINOMETHYL-SUBSTITUTED
1051
Under more rigid conditions that are required for
transformation of much less reactive dialkylamides
Ib and Ic bearing bulky substituents on the nitrogen
atom, especially in reaction with dibutylamine, addi-
tional signals appeared in the 31P NMR spectra of the
reaction mixture. This fact is probably explained by
partial decomposition of reaction products at high
temperatures. In detail, in the synthesis of compound
IIIb in boiling ethanol, along with the target product,
its decarbamoylation product Ph2P(O)CH2CH2NBu2
formed by deamination of the latter were isolated by
column chromatography and identified by H NMR
spectroscopy.
1
In an alternative procedure (method b) we em-
ployed preliminarily prepared tetraethylmethylenedi-
amine IV, bp 165 167 C, as dialkylaminomethylating
agent. This approach allowed reaction with the start-
ing dialkylamides to be accomplished at higher tem-
peratures (120 140 C) in the absence of solvent.
Method b was used to prepare products IIIa, IIIc, and
IIId.
(
32.04 ppm) and diphenyl(vinyl)phosphine oxide
P
Ph2P(O)CH=CH2
(
25.00 ppm, mp 125 126 C)
P
(b)
Ph2P(O)CH2C(O)NR2 + Et2NCH2NEt2
Ph2P(O)CHC(O)NR2
CH2NEt2
Ia Ic
IV
IIIa, IIIc, IIId
I, R = Et (a), i-Bu (b), Hex (c); II, R = Et (a), Bu (b); III, R = R = Et (a), R = Et, R = Bu (b), R = i-Bu, R = Et (c),
R = Hex, R = Et (d).
In the 31P NMR spectra of the reaction mixtures
we observed, along with the main signals of the
starting (amide) and final (aminoamide) products, an
In this case, the phase distribution of an extractant
is described by Eq. (2), where PL is the distribution
constant of the monomeric form of the extractant.
admixture signal at
25 26 ppm. This signal was
P
assigned to the phosphine oxide Ph2P(O)CH=CH2 that
is also probably formed by partial decomposition of
compounds IIIa IIIc under the reaction conditions.
At usual temperatures, the resulting aminoamides are
stable. They are crystalline (IIIa, IIIc) or oily (IIIb,
IIId) colorless substances. Their yields, methods of
D = PL + 2K2P 2L[L].
(2)
The values PL = 68 3 and K2 = 5.5 0.3 for
compound IIIa in 1,2-dichloroethane were calculated
by the least-squares procedure with the data in Fig. 1,
curve 2. In the water macroporous sorbent system,
extractant IIIa scarcely dimerizes in the concentration
range under study, and the distribution constant of the
monomeric form PL increases to 270 15.
synthesis, melting points, and H and 31P NMR spec-
1
tra are listed in Table 1.
In the present work we studied the extractive
ability of the synthesized dialkylaminomethyl-sub-
stituted dialkylamides of diphenylphosphinoylacetic
acid toward U(VI) and Pd(II) in nitrate media.
The effect of the nature of the organic solvent on
the extraction of U(VI) with compound IIIa from
nitrate solutions was studied (Table 2). The highest
DU value was obtained with nitrobenzene as solvent.
The weaker uranium extraction in the presence of
chloroform is evidently connected with the fact that
the activity of the extractant in the organic phase is
decreased due to P=O HCCl3 hydrogen bonding.
Note that the extraction of uranium with low-polarity
solvents (hexane, CCl4) is not weakened, whereas the
use of such solvents in the case of unsubstituted
carbamoylmethylphosphine oxides results in a much
weaker extraction [5].
From the 1,2-dichloroethane water distribution
data for compounds Ia and IIIa (Figs. 1, 2, and 3) it
follows that dialkylaminomethyl-substituted extractant
IIIa is more lipophilic than unsubstituted dialkyl-
amide Ia. It is noticeable that the distribution coef-
ficient D of extractant IIIa increases with its con-
centration in the organic phase. This is evidently
connected with partial dimerization of IIIa in the
organic phase with the dimerization constant K2
[Eq. (1), the components of the organic phase are
upperlined].
Increase in the concentration of NH4NO3 in the
aqueous phase enhances extraction of uranium into the
organic phase (Fig. 2), which is characteristic of
the extraction of uranyl nitrate solvates by Eq. (3).
K2
L2, K2 = [L2]/[L]2.
(1)
2L
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

1052
YARKEVICH et al.
Table 1. Yields, melting points, and 1H and 31P NMR spectra of compounds IIIa IIId
1H NMR spectrum, , ppm
Yield, %
31P NMR
spectrum,
P, ppm
mp,
C
(synthesis
method)
(hexane)a
PCH, PCCH2,
Alk2NC=O
Alk2N
Ph
m
br. m
IIIa
IIIb
75 (a)
71 (b)
64 65 0.84 t (3H), 0.89 t 0.96 t (6H, 2CH3); 3.80
3.00
7.46 m (6H), 7.88
m (2H), 8.30 m
(2H)
29.93
30.55
(3H) (2CH3); 3.26 q 2.32
(2H), 3.34 q (2H) 2.42
m
m
(2H),
(2H)
(2CH2)
0.86 t (6H, 2CH3); 0.88 t (6H, 2CH3); 3.78
2.34 m (2H), 1.22 (8H,
2.42 (2H)
(CH2NCH2)
(CH2NCH2)
b
63 (a)
74 (a)
2.95
3.08
7.48 m (6H), 7.90
m (2H), 8.30 m
(2H)
m
m
2CH2)2; 3.12 m
(2H), 3.32 m (2H)
(2CH2)
IIIc
IIId
89 92 0.78 m (6H, 2CH3); 0.90 t (6H, 2CH3); 3.82
7.48 m (6H), 7.90
m (2H), 8.26 m
(2H)
29.41
30.20
78 (b)
0.96 m (6H, 2CH3); 2.32
1.78 (1H), 2.52 m (2H)
1.94 m (1H) (2CH); (CH2NCH2)
2.82 (2H),
m
(2H),
m
m
3.18 m (2H) (2CH2)
0.88 m (6H, 2CH3); 0.88m(6H, 2CH3); 3.80
b
66 (b)
2.92
7.48 m (6H), 7.90
m (2H), 8.30 m
(2H)
1.24 m (16H,
(2CH2)4; 3.12 m
(2H), 3.32 m (2H)
(2CH2)
2.46 m (4H)
(CH2NCH2)
a
b
Solvent for crystallization.
Oil.
rithmic dependence of DU on extractant concentration
in dichloroethane, is 1:2 for all the compounds
studied (Fig. 3). At high concentrations of IIIa in the
organic phase, the slope of the logDU logCL de-
pendence decreases (Fig. 3, curve 5). This can be
connected both with the decrease of the fraction of
the monomeric form of the extractant with increasing
total concentration of the latter in the organic phase,
as well as with the formation of less hydrophobic
monosolvates UO2(NO3)2L with increasing concent-
ration of the extractant in the aqueous phase. The
dependence of DU on extractant concentration in
UO22++ 2NO3 + nL
UO2(NO3)2Ln
(3)
The extraction of U(VI) from nitric acid solutions
is appreciably weaker (Fig. 2), which is connected
with extractant HNO3 complex formation in the
organic phase and the resulting decrease in the con-
centration of the free extractant.
The U:L stoichiometric ratio in the extracted
uranyl nitrate solvate, as determined from the biloga-
Table 2. Distribution coefficient of U(VI) on extraction
with 0.01 M solutions of compound IIIa from 4 M
NH4NO3 solutions
equilibrium phases is given by Eq. (4), where
are
1,2
the stability constants of uranyl nitrate solvates and
PUO (NO )L , distribution constant of extracted solvate.
2
3
2
2PUO (NO ) L [L]2[NO3 ]2
Solvent
DU
Solvent
DU
2
3 2 2
DU =
.
(4)
P2L (1 + 1[L][NO3 ]2 + 2[L]2[NO3 ]2)
Nitrobenzene
Toluene
1,2-Dichlorobenzene 1.14 Chloroform
CCl4 0.78
5.54 Hexane
1.29 1,2-Dichloroethane 0.74
0.28
0.74
At a constant NH4NO3 concentration in the
aqueous phase, the highest DU value corresponds to
the distribution constant of extracted solvate
(PUO (NO ) L ). For the complex of U(VI) with IIIa in
2
3 2 2
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

SYNTHESIS AND EXTRACTIVE PROPERTIES OF DIALKYLAMINOMETHYL-SUBSTITUTED
1053
logDU
0.12
cL, M
1
1
2
0.5
0
0.10
0.08
2
0.5
0.06
0.04
0.02
0
3
1.0
1.5
0
1
2
3
4
5
c, M
1
2 3 4 5 6
7
8 9 10
[L] 104, M
Fig. 1. Dependence of the equilibrium concentration of
compounds (1, 2) IIIa and (3) Ia in (2, 3) 1,2-dichloro-
ethane or (1) macroporous sorbent phase (I) on the
equilibrium concentration of compounds Ia and IIIa in
the aqueous phase.
Fig. 2. Dependence of the distribution coefficient of
uranium on the concentration of (1) NH NO and
4
3
(2) HNO in the aqueous phase on the extraction of
3
uranium with 0.025 M solutions of compound IIIa in
1,2-dichloroethane.
dichloroethane it is equal to 26.3 2.5. More effective
extraction of uranium with extractant IIIa is achieved
by application of the latter on a macroporous sorbent
(Vofatit ER 60 styrene divinylbenzene copolymer)
(Fig. 3, plot 1), which is explained by increased
PUO (NO ) L in such systems. The advantages of
U(VI), Am(III) and Eu(III) from nitric acid solutions
on introduction of alkyl, benzyl, diethylaminopropyl,
and some other substituents into the methylene bridge
of tetraphenylmethylene dioxide and diphenyl(dialkyl-
carbamoylmethyl)phosphine oxides may be explained
by restricted conformational mobility of ligands
involved in complex formation [1, 11]. Furthermore,
the fairly high basicity of the nitrogen atom in the
CH2NR2 fragment of IIIa IIId enhances HNO3 ex-
traction with these reagents compared to unsubstituted
2
3 2
impregnate2d sorbent extraction of metal complexes
from aqueous solutions over liquid extraction have
repeatedly discussed in the literature [6 9].
The alteration of the extractive activity of com-
pounds IIIa IIId toward uranium is connected with
the alteration of the stability constants of the uranyl
nitrate disolvates formed, as well as by the alteration
of the distribution constants of these solvates. As the
lipophilicity of the ligand involved in complex forma-
tion increases with increasing size of the hydrocarbon
radicals on the amide nitrogen atoms and the dialkyl-
aminomethyl fragment, the extractive ability increases
in the series IIIa < IIIb < IIId. Replacement of ethyl
radicals at the amide nitrogen atom (compound IIIc
by isobutyls (compound IIIa) increases the lipophi-
licity of the ligand but adversely affects uranium
extraction, which is probably connected with steric
hindrances to complex formation and decreased
stability of the corresponding uranyl nitrate disovates.
logDU
1
1.5
2
1.0
0.5
5
3
4
6
0
0.5
1.0
2.6 2.4 2.2 2.0 1.8 1.6 1.4 1.2 1.0
log cL
(Diethylcarbamoylmethyl)diphenylphosphine oxide
(Ia) more effectively extracts U(VI) than reagent IIIa
(Fig. 3). This fact agrees with the notion that
Pearson’s hard ion UO22 is extracted as a coordinately
solvated uranyl nitrate. The decreased extraction of
Fig. 3. Dependence of the distribution coefficient of
uranium on the initial concentrations of compounds
(2) Ia, (1, 5) IIIa, (4) IIIb, (6) IIIc, and (3) IIIg in
(3 6) dichloroethane or (1) polymeric sorbent phase on
the extraction of uranium from 4 M solution of NH NO .
4
3
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

1054
log DPd
YARKEVICH et al.
log DPd
1
2
0
0
0.2
0.4
0.6
0.8
0.5
1.0
1.5
3
0
1
2
3
4
5
6
3
2.1 1.9 1.7
1.5 1.3 1.1
0.9
log cL
cNO , M
Fig. 4. Dependence of the distribution coefficient of
palladium on the concentration of (1) compound IIIa,
(2) trioctylamine, and (3) compound Ia in 1,2-dichlo-
Fig. 5. Dependence of the distribution coefficient of
palladium on the concentration of HNO in the aqueous
3
phase on extraction with 0.05 M solution of compound
roethane on extraction from 0.15 M HNO solution.
3
IIIa in chloroform.
dialkylamides Ia Ic, which appreciably decreases the
concentration of the free extractant in the organic
phase and decreases DU [Eq. (4)].
palladium are extracted with the protonated extractant
in the form of the [Pd(NO3)4]2 (HL+)2 complex by the
mechanism of extraction with amine salts [13].
Evidence for the formation of such an associate in the
organic phase comes from the observation in the elec-
tronic absorption spectrum, along with the band at
410 nm, of one more band at 325 nm. According to
[14], this additional band suggests that palladium is
extracted with amines in the form of a double salt
including the [Pd(NO3)4]2 anion.
On the other side, introduction of the CH2NEt2
fragment in amide Ia enhances extraction of Pearson’s
soft ion Pd2+ with reagent IIIa (Fig. 4). The apparent
solvation number for the extraction of Pd(II) with this
compound, estimated by the equilibrium shift method,
is 1.5, which implies extraction of 1:1 and 1:2 Pd:L
(IIIa) complexes. Under these experimental condi-
tions, DPd for the extraction with compound IIIa is
slightly higher than for the extraction of palladium
with trioctylamine (Fig. 4). This result is probably
connected with the formation of chelate ring A on the
extraction of palladium nitrate monosolvate. Such
chelate structures were previously used to explain
enhanced palladium extraction with tetraalkylethy-
lenes [12].
It is known that solvation of an amine salt with
nucleophilic reagents, associated with charge transfer
from the reagent on the hydrogen atom of the amine
salt, should increase the extractive ability of the latter
[13]. Actually, in the presence of diphosphine dioxide
Ph2P(O)(CH2)5P(O)Ph2 (S) in the organic phase, a
synergistic effect is observed on palladium extraction
with a mixture of reagents IIIa and S (Fig. 6). The
method of isomolar series was used to show the
highest synergism coefficient A = D/(D1 + D2) (D1,
D2, and D are the distribution coefficients for palla-
dium extraction with individual reagents and their
mixture, respectively) is observed at a 1:1 reagent
molar ratio in the organic phase (Fig. 6). It can be
proposed that the complex [Pd(NO3)4](HL)2 extracted
with compound IIIa in the presence of dioxide S is
transformed in an ionic associate containing S in the
anionic part of the complex.
O
NEt2
Ph
Ph
P
NEt2
O
Pd2+
A
On the extraction of palladium with compound IIIa
the distribution coefficient of palladium decreases
with increasing concentration of nitric acid in the
aqueous phase (Fig. 5), on account of competition of
HNO3 for the extractant. When the concentrations of
HNO3 is higher than 2 M, the DPd value slightly
increases, probably, because the anionic forms of
[Pd(NO3)4]2 (HL+)2 + S
[Pd(NO3)3S] (HL+) + HL NO3.
(5)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

SYNTHESIS AND EXTRACTIVE PROPERTIES OF DIALKYLAMINOMETHYL-SUBSTITUTED
This process is favored by increased concentration
1055
of compound S in the organic phase and decreased
concentration of nitric acid in the equilibrium aqueous
phase. Substitution of the NO3 ligand in the inner
coordination sphere of the complex Pd(II) anion with
S increases hydrophobicity of the extracted anionic
associate and may be one of the reasons for the ob-
served synergistic effect.
c
IIIa, M
0.02 0.0175 0.015 0.01 0.005 0.0025 0
A
DPd
1.0
3.0
3
0.8
2.5
4
The presented data show that substitution of the
hydrogen atom in the methylene bridge of N,N-di-
alkyl(diphenylphosphinoyl)acetamide with a dialkyl-
aminomethyl group may both decrease and increase
the extractive ability of the resulting compound,
depending on the nature of the ion to be extracted.
0.6
0.4
0.2
0
2.0
1.5
1.0
2
1
0.0025 0.005 0.01 0.015 0.0175 0.02
EXPERIMENTAL
cS, M
The H and 31P NMR spectra were registered for
1
CDCl3 solutions on a Bruker CXP spectrometer at
200 and 81 MHz, respectively, against internal TMS
and external H3PO4. The melting points were me-
asured on a Boetius PNMK-05 device. The concentra-
tion of uranium in the starting and equilibrium
aqueous solutions was measured on a KFK-2MP
photocolorimeter in the presence of Arsenazo III, and
the concentration of palladium in the aqueous solu-
tions was measured on the same device in the pre-
sence of nitroso-R-salt [15]. The concentrations of
extractants Ia and IIIa in the aqueous phase
were determined spectrophotometrically at 270 nm
on an SF-26 spectrophotometer. The electronic ab-
sorption spectra of the extracts were obtained on a
Specord UV VIS spectrophotometer.
Fig. 6. Extraction of palladium from 0.15 M HNO
solutions of (3) compound IIIa, (2) Ph P(O)(CH )
3
2
2 5
P(O)Ph , and (1) their isomolar mixtures in 1,2-dichloro-
2
ethane. (4) Synergism coefficient A.
The extraction and sorption experiments were
carried out at 18 2 C a 1:1 ratio of the organic and
aqueous phases for extraction and a 10:1 ratio of the
volume of the aqueous phase and the weight of the
sorbent for sorption. The phases were stirred for 1 h
until constant distribution coefficients.
The synthesis of Ph2P(O)CH2)5P(O)Ph2 [18] and
N,N-dialkyl(diphenylphosphinoyl)acetamides Ia, Ic
[2] and Ib [19] was described previously.
N,N-Diethyl-3-(diethylamino)-2-(diphenylphos-
phinoyl)propionamide (IIIa). a. A mixture of 1.58 g
of dialkylamide Ia, 0.73 g of diethylamine IIa, and
2 ml of 30% aqueous Formalin was stirred for 3 h at
60 C. After cooling to room temperature, the reaction
mixture was extracted with chloroform (3 15 ml).
The organic extracts were combined, washed with
water, and dried over sodium sulfate. The solvent was
removed in a vacuum, and the product was purified
by column chromatography on neutral alumina, eluent
15:1 hexane 2-propanol, to obtain 1.41 g of com-
pound IIIa, yield 75%.
Extraction equilibria were studied using nitro-
benzene, toluene, 1,2-dichlorobenzene, CCl4, hexane,
1,2-dichloroethane, and chloroform of pure or analy-
tical grades. The IIIa-impregnated sorbent was pre-
pared on a Vofatit EP 60 (Germany, Bitterfeld) non-
ionogenic
macroporous
styrene divinylbenzene
copolymer matrix. The principal characteristics of the
matrix are reported in [16]. The procedure of applica-
tion of extractant IIIa on Vofatit EP 60 is described
in [17].
The aqueous solutions of uranyl nitrate with the
4
initial concentration 5 10 M were prepared from
b. A mixture of 1.58 g of dialkylamide Ia and
1.58 g of Et2NCH2NEt2 (IV) was heated in an eva-
cuated ampule at 130 C for 2 h. Excess diamine was
removed in a vacuum. The reaction mixture was
cooled, and the product was purified by column
chromatography on neutral alumina, eluent 15:1
hexane 2-propanol to obtain 1.41 g (71%) of com-
pound IIIa.
the standard solutions of UO2(NO3)2, NH4NO3, and
HNO3, prepared from ultrapure grade chemicals. The
initial solutions of palladium nitrate were prepared by
dissolution of metallic palladium (palladium content
99.12%) in 3 M aqueous HNO3 at elevated tempera-
ture and subsequent dilution of the resulting solution
4
with water to a concentration of Pd2+ 5 10 g-ion/l.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 75 No. 7 2005

1056
YARKEVICH et al.
N,N-Diethyl-3-(dibutylamino)-2-(diphenylphos-
4. Bondarenko, N.A. and Tsvetkov, E.N., Zh. Obshch.
Khim., 1989, vol. 59, no. 7, p. 1533.
phinoyl)propionamide (IIIb). A mixture of 0.63 g
of dialkylamide Ia, 0.52 g of dibutylamine IIb, and
0.5 ml of 30% aqueous Formalin in 2 ml of ethanol
was stirred under slight reflux for 3 h. The reaction
mixture was cooled to room tempeature and extracted
with chloroform. The combined organic fractions were
washed with water and dried over sodium sulfate. The
solvent was removed in a vacuum, and the residue
was extracted with dry hexane to remove diphenyl-
(vinyl)phosphine oxide (0.07 g, yield 16%). The
organic extract was concentrated and subjected to
column chromatography on neutral alumina. Elution
with hexane gave 0.09 g (12%) of Ph2P(O)CH2CH2
NBu2, and elution with 20:1 hexane 2-propanol gave
0.57 g of compound IIIb, yield 63%.
5. Rozen, A.M., Nikiforov, A.S., Nikolotova, Z.I., and
Kartasheva, N.A., Dokl. Akad. Nauk SSSR, 1986,
vol. 286, no. 3, p. 667.
6. Flett, D.S., Chem. Ind., 1977, no. 6, pp. 641 646.
7. Meretukov, M.A., Ispol’zovanie impregnirovannykh
materialov dlya izvlecheniya i rasdeleniya tsvetnykh
metallov (Use of Impregnated Materials for Extraction
and Separation of Nonferrous Metals), TsNIIEITsM
Reviews, 1980, no 3, p. 49.
8. Warshawsky, A., Solv. Extr. Ion Exch., 1981, vol. 8,
p. 229.
9. Cortina, J.L., and Warshawsky, A., Solv. Extr. Ion
Exch., 1997, vol. 13, p. 195.
10. Rozen, A.M. and Krupnov, V.V., Usp. Khim., 1996,
N,N-Diisobutyl-3-(diethylamino)-2-(diphenyl-
phosphinoyl)propionamide (IIIc) was obtained
analogously to compound IIIa by method a from
0.93 g of diisobutylamide IIIb, 0.73 g of Et2NH, and
1 ml of 30% aqueous Formalin (60 C, 3 h), and by
method b from 0.93 g of diisobutylamide IIIb and
0.79 g of diamine IV (140 C, 6 h).
vol. 65, no. 11, pp. 1052 1079.
11. Shadrin, A.Yu., Smirnov, I.V., Kiseleva, R.N., Neste-
rova, H.P., Polikarpov, Yu.M., and Kabachnik, M.I.,
Radiokhimiya, 1993, vol. 35, no. 1, pp. 50 56.
12. Belova, V.V., Khol’kin, A.I., Vasilevich, S.A., Zhid-
kova, T.I., Medkov, M.A., Shipunov, Yu.A., and
Shumilina, E.V., Zh. Neorg. Khim., 1994, vol. 39,
no. 11, p. 1856.
N,N-Dihexyl-3-(diethylamino)-2-(diphenylphos-
phinoyl)propionamide (IIId) was obtained analog-
ously to compound IIIa by method b from 1.07 g of
dihexylamide IIIc and 0.79 g of diamine IV (120 C,
6 h).
13. Shmidt, V.S., Ekstraktsiya aminami (Extraction with
Amines), Moscow: Atomizdat, 1980, p. 262.
14. Shmidt, V.S., Shorokhov, N.A., and Novikova, S.S.,
Zh. Neorg. Khim., 1984, vol. 29, no. 3, p. 773.
ACKNOWLEDGMENTS
15. Ginzburg, S.I., Ezerskaya, N.A., Prokof’eva, I.V.,
Fedorenko, N.V., Shlenskaya, V.I., and Bel’skii, N.K.,
Analiticheskaya khimiya platinovykh metallov (Analyt-
ical Chemistry of Platinum Metals), Moscow: Nauka,
1972.
The authors express their sincere gratitude to
V.O. Zavel’sky and A.N. Pushin for registration and
discussion of the NMR spectra.
16. Kremenskaya, I.N., Turanov, A.N., Myul’, P., and
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