Simple route to secondary amides of phosphorylacetic acids and their use for extraction and sorption of actinides from nitric acid solutions

Article abstract of DOI:10.1007/s11172-005-0146-2

An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids (APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary aliphatic amines. The scope of reaction was determined. Reactions with ethy

Full text of DOI:10.1007/s11172-005-0146-2

Russian Chemical Bulletin, International Edition, Vol. 53, No. 11, pp. 2499—2507, November, 2004
2499
Simple route to secondary amides of phosphorylacetic acids
and their use for extraction and sorption of actinides
from nitric acid solutions
a
a
a
b
O. I. Artyushin,a E. V. Sharova, I. L. Odinets, S. V. Lenevich, V. P. Morgalyuk,
ꢀ
I. G. Tananaev,b G. V. Pribylova,b G. V. Myasoedova,b T. A. Mastryukova,a and B. F. Myasoedovb
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
28 ul. Vavilova, 119991 Moscow, Russian Federation.
Fax: +7 (095) 135 5085. Eꢀmail: odinets@ineos.ac.ru
bInstitute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences,
19 ul. Kosygina, 119991 Moscow, Russian Federation
An efficient method for the synthesis of secondary alkylamides of phosphorylacetic acids
(APA) was proposed. The method involves amidation of ethyl phosphorylacetates with primary
aliphatic amines. The scope of reaction was determined. Reactions with ethylenediamine and
1,4ꢀdiaminobutane yield the corresponding bisamides; in the case of 1,3ꢀdiaminopropane,
Nꢀ(3ꢀaminopropyl)diphenylphosphorylacetamide or N,N´ꢀpropylenebis(diphenylphosphorylꢀ
acetamide) was obtained, depending on the reaction conditions. The extraction of americium(III)
complexes and the sorption of uranium(VI) by sorbents with physically sorbed APA from nitric
acid solutions were studied. There is no correlation between the partition coefficient of
americium(III) and the structure of APA; in the sorption of uranium(VI), the degree of extracꢀ
tion depends on the complexone structure.
Key words: amines, alkylenediamines, phosphorylacetates, ethyl diphenylphosphorylacetate,
phosphorylacetamides, carbamoylmethylphosphine oxides, actinides, americium, uranium,
extraction, sorption.
Development of nuclear industry and processing of
accumulated liquid radioactive wastes necessitates selecꢀ
tive extraction of longꢀlived isotopes (primarily, actinides).
For this purpose, liquidꢀliquid extraction with neutral orꢀ
ganophosphorus complexones, e.g., N,Nꢀdialkylphosꢀ
phorylacetamides (soꢀcalled carbamoylmethylphosphine
oxides (CMPO)), is widely used in current practice.1,2
Their main advantages are that actinides can be quantitaꢀ
tively recovered from highly active saltꢀcontaining wastes
(HAW) over a wide range of nitrogen acid concentrations
without its preliminary correction and that CMPO are
well compatible with various solvents. The soꢀcalled
TRUEX process has been developed in the USA for fracꢀ
tionation of HAW with the use of N,Nꢀdiisobutylcarbaꢀ
moylmethyl(octylphenyl)phosphine oxide.2 Its versions
were proposed in Japan and Italy. In Russia,3 this techꢀ
nique was tested in processing of real wastes differing in
origin and composition with N,Nꢀdibutylcarbamoylꢀ
methyl(diphenyl)phosphine oxide.4 At the same time,
methods for sorption concentration of actinides from niꢀ
tric acid media with sorbents (solid extractants) bearing
selective complexone groups physisorbed on a polymer
matrix are presently under intense development.5,6 Use of
CMPO in such sorbents makes it possible to extract acꢀ
tinides from nitric acid solutions with high partition coefꢀ
ficients.7,8
In recent years, CMPO containing the secondary
amide fragment —C(O)NHR are of growing interest. The
presence of the hydrogen atom at the N atom makes the
CMPO molecule hydrophilic and can change the characꢀ
ter of complexation with actinide ions and the sorption
process as a whole. One can expect that the hydrophilic
amide group in secondary alkylamides of phosphorylacetic
acids (APA) will increase the hydrophilicity of sorbents
bearing noncovalently fixed APA at the polymer matrix,
thus promoting the sorption of actinides.
In particular, lanthanide and actinide ions were effiꢀ
ciently extracted from nitric acid media with compounds
containing the fragments NHC(O)CH2P(O)Ph2 fixed on
the upper rims of the calix[4]ꢀ and calix[5]arene rings,9
the C3ꢀsymmetrical triphenoxymethane framework,10 and
the carborane fragment.11 However, such compounds are
not easily accessible and no promising route to APA has
been found to date. In addition, studies of the extraction
and sorption of actinides by the aforesaid compounds
containing alkyl substituents have not been documented.
During our investigations directed to syntheses of new
types of CMPO and their complexation with f elements,12
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2394—2402, November, 2004.
1066ꢀ5285/04/5311ꢀ2499 © 2004 Springer Science+Business Media, Inc.

2500
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004
Artyushin et al.
Scheme 3
we proposed a simple and efficient method for the synꢀ
thesis of APA containing the secondary amide fragꢀ
ment —C(O)NHR and estimated the possibility of using
them for extraction and sorption concentration of acꢀ
tinides with AmIII and UVI as examples.
Usually, phosphorylacetamides are prepared by the
Arbuzov or Michaelis—Becker reaction of chloroꢀ
acetamides with appropriate phosphorus(III) derivatives
(Scheme 1).1,13,14
Alk = Et (a), Bun (b), Bui (c), nꢀC6H13 (d), nꢀC8H17 (e),
CH2CH(Et)Bu (f), nꢀC9H19 (g), nꢀC10H21 (h),
nꢀC12H25 (i), (CH2)2Ph (j),
(k)
Scheme 1
ing an alkyl substituent at the N atom, while secondary,
alkylaromatic, and aromatic amines cannot be involved
in this reaction. However, when the heterocyclic or aroꢀ
matic fragment and the N atom in an amine molecule are
separated by at least two methylene groups, the reaction
easily occurs to give the corresponding amides (2j,k).
When the P atom in the starting ester bears at least one
alkoxy group, the reaction is nonselective, yielding
products with amide fragments at both C and P atoms.
The 31P NMR spectrum contains two signals of nearly
equal intensity: the signal for the carbamide with the
phenyl(alkoxy) group at the P atom is shifted downfield
by ~4.5 ppm relative to the signal for the starting ethyl
phosphorylacetate and the higherꢀfield signal for the corꢀ
responding phosphinic acid amide. The amidation proꢀ
ceeds selectively only for sufficiently long radicals R in
the alkoxy group RO at the phosphorus atom (Scheme 4).
The amidation of ethyl phosphorylacetates 1a—c at
20 °C in ethanol was completed over ~10 days to give the
target secondary amides 2a—n in virtually stoichiometric
yields. However, heating of a reaction mixture (in the
presence of a small excess of the amine) in ethanol or
without a solvent in a sealed tube at 100 °C for 8—10 h is
more economical. The yields of analytically pure amides
2a—k containing a phosphine oxide fragment were 68
to 92%. Phosphinates 2l—n needed purification by chroꢀ
matography, and their yields were reduced to 36—56%.
Reactions of alkylenediamines with ethyl diphenylꢀ
phosphorylacetate 1a involve either one or both N atoms,
depending on the reaction conditions and the number of
methylene groups n in the alkylene fragment (Scheme 5).
Monoamides (3) were prepared in dilute ethanol at
room temperature; however, for even numbers n, the reꢀ
action is slow and the yields of monoamides (3a) and (3c)
(from 1,2ꢀethylenediamine and 1,4ꢀdiaminobutane, reꢀ
spectively) was at most 8 to 9% even for prolonged reacꢀ
tion times. In contrast, amide 3b was isolated in high
yield (77%). An increase in the reaction temperature in
EtOH leads to the nonselective formation of a mixture of
amides 3 and 4. With benzene as a solvent, bisamides 4
are the major products, irrespectively of the ratio between
the starting reagents and the n value. Also, bisamides 4 are
predominantly formed in hot concentrated ethanol over
several hours. To obtain compounds 4a—c in high yields,
B is the base
Earlier,9,11,15 pꢀnitrophenyl diphenylphosphorylꢀ
acetate was found to undergo amidation into secondary
amides (Scheme 2). This method involves only one orgaꢀ
nophosphorus substrate. However, pꢀnitrophenyl phosꢀ
phorylacetates are prepared in three steps from commerꢀ
cial ethyl esters, which substantially makes this method
less advantageous.
Scheme 2
R = Pri, Bui, nꢀC8H17, (CH2)5NH2
Use of commercially accessible phosphorusꢀcontainꢀ
ing reagents would make the synthesis cheaper and allow
one to obtain a broad range of compounds at minimum
costs.
We found that easily accessible ethyl diphenylphosꢀ
phorylacetate (1a) can also undergo amidation in reacꢀ
tions with primary amines in ethanol (Scheme 3).
The yields of secondary amides (2) are nearly stoꢀ
ichiometric. The method is preparatively simple since a
variety of secondary amides can be obtained from one
organophosphorus reagent and a number of amines.
Although the amidation of carboxylates is well known,
the study of the limits of its application showed that ester
1a reacts in such a way only with primary amines containꢀ

Synthesis of Nꢀalkylphosphorylacetamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004 2501
Scheme 4
Scheme 5
n = 2 (a), 3 (b), 4 (c)
it is expedient to use the starting reagents in a stoichioꢀ
metric ratio.
The 31P NMR spectra of compounds 2—4 show sinꢀ
glets at δ 30.08—34.72 for the corresponding phosphine
oxides and at δ 38.29—38.34 for phosphinates 2l—n, which
are characteristic of this environment of the P atom. Usuꢀ
ally, signals for amides 2—4 are shifted downfield comꢀ
pared to signals for the starting esters 1a—c. Note that the
chemical shifts for bisamides 4 are greater than those for
compounds 3. The structures of the compounds obtained
A distinctive feature of bisamides 4 is that these comꢀ
pounds with even and odd numbers n sharply differ in
solubility. Products 4a,c are poorly soluble in organic
solvents; they can be recrystallized from DMF, while
bisamide 4b (n = 3) is well soluble in most organic solꢀ
vents, except for benzene and diethyl ether.
The compositions and structures of products 2a—n, 3,
and 4a—c were confirmed by elemental analysis data
(Table 1) and IR and NMR spectra (Table 2). Earlier,16
Nꢀethyl(diphenylphosphoryl)acetamide 2a was obtained
in 63% yield by the Arbuzov reaction from Nꢀethylꢀ
chloroacetamide and ethyl diphenylphosphinate; howꢀ
ever, the spectroscopic data for this compound were missꢀ
ing.16 Amides 2c,e obtained earlier11 from pꢀnitrophenyl
diphenylphosphorylacetate were characterized only by IR
and 1H NMR spectra.
The IR spectra of alkylamides 2a—n, 3, and 4a—c
(KBr) show characteristic absorption bands at 1660—1680
(C=O) and 1180—1190 (P=O, 2a—k) or 1205—1230 cm–1
(P=O, 2l—n). The phosphoryl group in amides 2l—n
manifests itself as two peaks corresponding to the stretchꢀ
ing vibrations of free and hydrogenꢀbound P=O fragꢀ
ments. The NH group absorbs at 3180—3260 (ν(NH), br)
and 1540—1560 cm–1 (δ(NH) + and ν(C—N)). For the
reported11 amides 2c,e, the latter band was erroneously
assigned to the amide CO vibrations. On the whole, the
IR spectra of the secondary amides obtained are similar,
except for the vibrations of the corresponding alkyl groups
in the substituent R.
1
were confirmed by H NMR spectra containing, along
with characteristic sets of signals for the corresponding
substituents at the P and N atoms, signals for the PCH2
protons at δ 3.29—3.71 as a doublet (J = 11.7—13.9 Hz)
for compounds 2a—k, 3, and 4a—c (magnetically equivaꢀ
lent) or as a multiplet for compounds 2l—n with an asymꢀ
metric P atom (magnetically nonequivalent).
Thus, we demonstrated that ethyl diphenylphosphorylꢀ
acetate can be easily and efficiently converted into the
corresponding secondary amides by amidation with priꢀ
mary aliphatic amines.
Then, we studied extraction of americium(III) with
0.1 M solutions of APA 2b,c,e—h,i in dichloroethane from
nitric acid media. The results obtained are shown in Fig. 1.
The highest partition coefficient of AmIII (DAm) was atꢀ
tained at [HNO3] = 3 mol L–1 for all the compounds.
APA 2b,e,g,h,i with unbranched alkyl substituents are apꢀ
proximately equal in extraction ability toward AmIII. They
are as effective as N,Nꢀdialkylcarbamoylmethyl(dipheꢀ
nyl)phosphine oxides,17,18 for which the partition coeffiꢀ
cient also is insensitive to the structure of the substituent
at the N atom.18 However, APA 2c,f with branched subꢀ
stituents are noticeably inferior to compounds with nꢀalkyl

2502
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004
Artyushin et al.
Table 1. Yields and elemental analysis data for amides 2a—n, 3b, and 4a—c
Comꢀ
pound
R
R´
Yield (%)
M.p./°C
(benzene)
Found
Calculated
Molecular
formula
(%)
C
H
N
2aа
2b
Ph
Ph
Et
89
87
163
156—157
—
—
—
—
Bun
68.81
68.56
68.76
68.56
69.91
69.95
71.28
71.14
70.96
71.14
71.70
71.66
72.09
72.15
73.18
73.21
72.95
72.71
65.31
65.27
65.45
65.37
66.71
66.81
68.09
68.06
63.72
64.55
66.09
66.17
66.52
7.16
7.03
7.09
7.03
7.64
7.63
8.19
8.14
8.14
8.14
8.49
8.37
8.68
8.58
8.97
8.74
6.04
6.10
7.12
7.04
9.31
9.33
9.74
9.68
10.01
9.99
6.72
6.69
5.55
5.55
5.75
5.77
5.98
5.98
4.55
4.44
4.46
4.44
3.90
4.08
3.71
3.77
3.81
3.77
3.60
3.63
3.57
3.51
3.18
3.28
3.79
3.85
6.92
7.25
3.81
3.81
3.54
3.54
3.31
3.31
8.53
8.86
5.07
5.14
5.01
5.02
4.95
4.89
C18H22NO2P
2cb
2d
2eb
2f
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Bui
nꢀC6H13
92
85
72
74
68
70
75
78
77
56
42
36
77
172—173
147—148
149—150
147—148
C18H22NO2P
С20Н26NO2P
C22H30NO2P
C22H30NO2P
C23H32NO2P
C24H34NO2P
C26H38NO2P
C22H22NO2P
C21H27N2O3P
C20H34NO3P
C22H38NO3P
C24H42NO3P
C17H21N2O2P
C30H30N2O4P2
C31H32N2O4P2
C32H34N2O4P2
nꢀC8H17
BunCH(Et)CH2—
nꢀС9Н19
2g
2h
2i
141—142
(xylene)
146—147
(xylene)
134—135
nꢀС10Н21
nꢀС12Н25
2j
—(CH2)2Ph
214—215
188—189
2k
2l OCH2CH(Et)Bu
2m OCH2CH(Et)Bu
2n OCH2CH(Et)Bu
Bun
72—73
(hexane)
84—85
(hexane)
77—78
(hexane)
134—135
(С6H6)
280—281
(DMF)
nꢀC6H13
nꢀC8H17
3b
4a
4b
4c
Ph
Ph
Ph
Ph
—(СН2)3NH2
—(СН2)2NHC(O)CH2P(O)Ph2 40
—(СН2)3NHC(O)CH2P(O)Ph2 38
—(СН2)4NHC(O)CH2P(O)Ph2 33
173 (EtOAc;
C6Н6; C6Н6/CCl4) 66.66
240—241
(DMF)
67.21
67.13
a Ref. 16: m.p. 161—162 °C.
b The IR and 1H NMR spectra are reported in Ref. 11.
substituents in extraction ability toward AmIII. Earlier,19
the negative effect on the extraction of actinides was
reported for acidic and neutral organophosphorus
extractants with branched alkyl substituents in the alkoxy
group at the P atom.
The simplicity of the synthesis of APA with nꢀalkyl
substituents makes them promising for extraction of acꢀ
tinides from nitric acid media.
In addition, we studied the sorption of uranium(VI)
from nitric acid solutions by sorbents bearing nonꢀ
covalently fixed APA 2a,b,d,e,g,h as complexones with
diphenylphosphoryl group at the P atom. The correspondꢀ
ing sorbents with [complexone] = 0.26 mmol L–1 g–1
were prepared by physisorption of APA at an Amberlite
XADꢀ7TM macroporous acrylate matrix (particle size
0.2—0.5 mm).20,21 Uranium(VI) was sorbed from
5 M HNO3. The results obtained are shown in Fig. 2. It
can be seen that the sorption of UVI increases with the
lengthening of the substituent at the N atom, reaching the
maximum value for each compound upon a 2ꢀh contact
between the phases. For Nꢀethyl (2a), Nꢀnonyl (2g), and
Nꢀdecyl derivatives (2h), the sorption of UVI over 24 h is
lower than that reached in 2 h, which can be due to partial
"washout" of the complexones from the polymer matrix to
a nitric acid solution during their prolonged contact. For
sorbents with physisorbed Nꢀbutyl (2b), Nꢀhexyl (2d),
and Nꢀoctyl APA (2e), the degree of sorption of UVI
reached over 2 h does not decline with time (24 h); this

Synthesis of Nꢀalkylphosphorylacetamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004 2503
Table 2. 31P and 1H NMR and IR spectra of amides 2a—n, 3b, and 4a—c of the formula PhRP(O)CH2C(O)NHR´
Comꢀ
pound
R
R´
NMR (CDCl3)
1H NMR, δ, J/Hz
IR, ν/cm–1
δ
ν
ν
ν
NH
P
P=O
C=O
3
2a
Ph
Et
32.21
0.98 (t, 3 H, Me, JH,H = 7.3); 3.18 (br.s,
1165 1670
3290,
1550
2 H, NCH2); 3.44 (d, 2 H, PCH2,
2JP,H = 12.8); 5.60 (br.s, 1 H, NH);
7.46—7.57 (m, 6 H, pꢀ and mꢀC6H5P);
7.73—7.78 (m, 4 Н, oꢀС6H5P)
3
2b
Ph
Bun
31.26
0.80 (t, 3 H, Me, JH,H = 7.3); 1.17—1.24
1187 1662
3280,
1560
(m, 2 H, NHCH2CH2CH2Me); 1.32—1.39
(m, 2 H, NHCH2CH2CH2Me); 3.18 (q*,
2 H, NCH2, 3JH,H = 3JH,H = 6.6); 3.29 (d,
2 H, PCH2, 2JP,H = 12.4); 7.46—7.56 (m,
6 H, pꢀ and mꢀC6H5P); 7.70—7.74 (m, 4 Н,
oꢀС6H5P); 7.35 (br.s, 1 H, NH)
3
2c
2d
Ph
Ph
Bui
33.25
34.72
0.77 (d, 6 H, Me, JH,H = 6.7); 1.62—1.68
1170 1680
3310,
1545
(m, 1 H, CH); 3.00 (br.d, 2 H, NCH2,
3JH,H = 5.5); 3.53 (d, 2 H, PCH2,
2JP,H = 13.2); 7.48—7.58 (m, 6 H,
pꢀ and mꢀC6H5P); 7.75—7.80 (m, 4 Н,
oꢀС6H5P); 7.92 (br.s, 1 H, NH)
3
nꢀC6H13
0.83 (t, 3 H, Me, JH,H = 6.7); 1.17—1.23
1180 1670
3290,
1545
(m, 6 H, NHCH2CH2(CH2)3Me); 1.34—1.37
(m, 2 H, NHCH2CH2); 3.14—3.17 (m, 2 H,
NCH2); 3.62 (d, 2 H, PCH2, 2JP,H = 13.2);
7.49—7.59 (m, 6 H, pꢀ and mꢀC6H5P);
7.77—7.82 (m, 4 Н, oꢀС6H5P);
8.13 (br.s, 1 H, NH)
3
2e
2f
Ph
Ph
Ph
Ph
nꢀC8H17
BunCH(Et)CH2—
nꢀC9H19
34.07
30.08
30.01
30.05
0.86 (t, 3 H, Me, JH,H = 6.8); 1.17—1.26
1175 1670
1190
3320
1555—1560
(m, 10 H, NHCH2CH2(CH2)5Me);
1.35—1.39 (m, 2 H, NHCH2CH2);
3.13—3.17 (m, 2 H, NCH2); 3.57 (d, 2 H,
PCH2, 2JP,H = 13.2); 7.49—7.59 (m, 6 H,
pꢀ and mꢀC6H5P); 7.76—7.81 (m, 4 Н,
oꢀС6H5P); 8.01 (br.s, 1 H, NH)
0.75 and 0.82 (both t, 6 H, Me, JH,H = 7.0); 1185 1660
1.15—1.33 (m, 9 H,
3
3280,
1555
NHCH2CH(СН2СН3)(CH2)3Me);
3.12—3.15 (m, 2 H, NCH2); 3.30 (d, 2 H,
PCH2, 2JP,H = 12.2); 7.36 (br.s, 1 H,
NH); 7.47—7.55 (m, 6 H, pꢀ and mꢀC6H5P);
7.70—7.75 (m, 4 Н, oꢀС6H5P)
3
2g
2h
0.88 (t, 3 H, Me, JH,H = 6.7); 1.17—1.27
(m, 12 H, NHCH2CH2(CH2)6Me);
1.37—1.38 (m, 2 H, NHCH2CH2); 3.15—3.20
(m, 2 H, NCH2); 3.29 (d, 2 H, PCH2,
2JP,H = 12.3); 7.34 (br.s, 1 H, NH);
7.46—7.56 (m, 6 H, pꢀ and mꢀC6H5P);
7.70—7.74 (m, 4 Н, oꢀС6H5P)
1190 1660
3290,
1555
3
nꢀC10H21
0.86 (t, 3 H, Me, JH,H = 6.8); 1.16—1.28
1185 1660
3290,
1555
(m, 14 H, NHCH2CH2(CH2)7Me);
1.36—1.37 (m, 2 H, NHCH2CH2);
3.14—3.19 (m, 2 H, NCH2); 3.29 (d, 2 H,
PCH2, 2JP,H = 12.4); 7.36 (br.s, 1 H, NH);
7.44—7.56 (m, 6 H, pꢀ and mꢀC6H5P);
7.72—7.83 (m, 4 Н, oꢀС6H5P)
(to be continued)

2504
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004
Artyushin et al.
Table 2 (continued)
Comꢀ
pound
R
R´
NMR (CDCl3)
1H NMR, δ, J/Hz
IR, ν/cm–1
δ
ν
ν
ν
NH
P
P=O
C=O
3
2i
Ph
nꢀC12H25
30.11
0.87 (t, 3 H, Me, JH,H = 6.4); 1.12—1.28
1190 1660
3290,
1545
(m, 14 H, NHCH2CH2(CH2)9Me);
1.32—1.40 (m, 2 H, NHCH2CH2);
3.14—3.19 (m, 2 H, NCH2); 3.29 (d, 2 H,
PCH2, 2JP,H = 12.3); 7.35 (br.s, 1 H, NH);
7.48—7.56 (m, 6 H, pꢀ and mꢀC6H5P);
7.69—7.74 (m, 4 Н, oꢀС6H5P)
2j
Ph
Ph
—(CH2)2Ph
31.07 2.60 (br.s, 1 H, NH); 2.67—2.71 (m, 2 H,
NHCH2CH2); 3.32 (d, 2 H, PCH2,
2JP,H = 11.7); 3.43 (br.s, 2 H, NCH2);
7.11—7.24 (m, 5 H, NCH2CH2C6H5);
7.35—7.55 (m, 6 H, pꢀ and mꢀC6H5P);
7.67—7.78 (m, 4 Н, oꢀС6H5P)
30.60 1.78 (pentet, 2 H, NCH2CH2, 3JH,H = 6.3);
3.85 (br.s, 4 H, —CH2—O—CH2—);
3.35 (d, 2 H, PCH2, 2JP,H = 12.6);
1190 1660
3268,
1555
2k
1185 1670
3290,
1550
3.28—3.33 (m, 2 H, NCH2); 2.52—2.77
(two m, 6 H, —CH2—N—(CH2)(CH2)—);
7.46—7.49 (m, 6 H, pꢀ and mꢀC6H5P);
7.69—7.81 (m, 4 Н, oꢀС6H5P);
7.87 (br.s, 1 H, NH)
38.34 0.80—0.90 (three t**, 9 H, Me); 1.14—1.54
2l OCH2CH(Et)Bu
2m OCH2CH(Et)Bu
2n OCH2CH(Et)Bu
Bun
1210, 1660
3280,
1554
(m, 13 H, nꢀMe(CH2)3CH(СН2СН3)CH2О—,1230
NHCH2CH2CH2Me); 2.87—3.06 (m, 2 H,
PCH2); 3.21 (q*, 2 H, NCH2, 3JH,H = 4.8);
3.66—3.74 and 3.89—3.95 (two m, 2 Н,
MeСН2О); 7.07 (br.s, 1 H, NH);
7.46—7.59 (m, 3 H, pꢀ and mꢀC6H5P);
7.72—7.77 (m, 2 Н, oꢀС6H5P)
nꢀC6H13
38.29 0.81—0.86 (three t***, 9 H, Me); 1.15—1.55 1205, 1661
(m, 17 H, nꢀMe(CH2)3CH(СН2СН3)CH2О—,1225
NHCH2CH2(CH2)3Me); 2.88—3.06 (m,
2 H, PCH2); 3.18—3.24 (m, 2 H, NCH2);
3.69—3.75 and 3.90—3.97 (two m, 2 Н,
MeСН2О); 7.05 (br.s, 1 H, NH);
3276,
1555
7.47—7.60 (m, 3 H, pꢀ and mꢀC6H5P);
7.73—7.78 (m, 2 Н, oꢀС6H5P)
nꢀC8H17
38.29 0.80—0.87 (three t***, 9 H, Me); 1.15—1.54 1205, 1661
(m, 21 H, nꢀMe(CH2)3CH(СН2СН3)CH2О—,1225
NHCH2CH2(CH2)5Me); 2.87—3.05 (m,
2 H, PCH2); 3.17—3.23 (m, 2 H, NCH2);
3.68—3.73 and 3.91—3.96 (two m, 2 Н,
MeСН2О); 7.06 (br.s, 1 H, NH);
3274,
1555
7.48—7.61 (m, 3 H, pꢀ and mꢀC6H5P);
7.72—7.79 (m, 2 Н, oꢀС6H5P)
3b
Ph
—(СН2)3NH2
30.13 1.50 (quint, 2 H, NHCH2CH2CH2NH2,
3JH,H = 6.6); 1.54—1.69 (m, 3 H,
NH2 + NH); 2.54 (t, 2 H, —CH2NH2,
3JH,H = 6.8); 3.27 (q, 2 H, —NHCH2,
3JH,H = 6.2); 3.29 (d, 2 H, PCH2,
2JP,H = 12.1); 7.47—7.55 (m,
1185 1655 3242 br,
1562 br
6 H, pꢀ and mꢀC6H5P);
7.70—7.73 (m, 4 Н, oꢀС6H5P)
(to be continued)

Synthesis of Nꢀalkylphosphorylacetamides
Table 2 (continued)
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004 2505
Comꢀ
pound
R
R´
NMR (CDCl3)
1H NMR, δ, J/Hz
IR, ν/cm–1
δ
ν
ν
ν
NH
P
P=O
C=O
4a*** Ph —(СН2)2NHC(O)CH2P(O)Ph2 29.39 3.15 (br.s, 4 H, NH(CH2)2NH);
3.71 (d, 4 H, PCH2, 2JP,H = 13.9);
1176 1662
3271,
1558
7.59—7.67 (m, 12 H, pꢀ and mꢀC6H5P);
7.90—7.95 (m, 8 H, o ꢀC6H5P);
8.41 (br.s, 2 H, NH)
4b
Ph —(СН2)3NHC(O)CH2P(O)Ph2 32.77 1.71 (quint, 2 H, NHCH2CH2CH2NH,
1173 1667 3258 br,
1541 br
3JH,H = 6.8); 3.35 (q, 4 H,
3
NHCH2CH2CH2NH, JH,H = 5.4);
3.61 (d, 4 H, PCH2, 2JP,H = 13.6);
7.32—7.37 (m, 8 H, pꢀC6H5P);
7.46—7.49 (m, 4 H, mꢀC6H5P);
7.62—7.66 (m, 8 Н, oꢀС6H5P);
9.03 (br.s, 2 H, NH)
4c*** Ph —(СН2)4NHC(O)CH2P(O)Ph2 28.94 1.30 (br.s, 4 H, NHCH2(CH2)2CH2NH);
3.05 (br.s, 4 H, NHCH2(CH2)2CH2NH);
3.69 (d, 4 H, PCH2, 2JP,H = 13.1);
1179 1663
3284
1547,
7.59—7.65 (m, 12 H, pꢀ and mꢀC6H5P);
7.91—7.93 (m, 8 H, oꢀC6H5P);
8.19 (br.s, 2 H, NH)
* The discernible quartet.
** The overlapping triplets.
*** The 1H and 31P NMR spectra were recorded in DMFꢀd7.
logDAm
Sorption of UVI (%)
100
80
0.8
0.4
1
0
2
60
–0.4
–0.8
–1.2
–1.6
1
2
3
4
5
6
7
40
20
2
4
6
8
Cn
1
2
3
4
5
[HNO3]/mol L–1
Fig. 2. Sorption of uranium(VI) (%) from 5 M HNO3 by sorbents
with physically sorbed Nꢀalkylcarbamoylmethyl(diphenyl)phosꢀ
phine oxides 2a,b,d,e,g,h differing in the length of the alkyl
radical at the N atom (R = nꢀC2—C10); static conditions, the
initial concentration [UO22+] = 10 mg L–1, V/m = 500 mL g–1
phase contact time was (1) 2 and (2) 24 h.
Fig. 1. Extraction curves of AmIII at different [HNO3] values.
The extractants are 0.1 M solutions of APA 2b,c,e—h,i in
dichloroethane: (1) Bun, (2) nꢀOct, (3) nꢀNon, (4) nꢀDec,
(5) nꢀDodec, (6) Bui, and (7) 2ꢀEtHex.
;
can probably be attributed to the low solubilities of these
compounds in nitric acid. Apparently, the sorption equiꢀ
librium of UVI between the contacting phases is estabꢀ
lished within the first two hours.
The data on the extraction of uranium and the rate at
which the equilibrium is established suggest that the sorꢀ
bent containing Nꢀoctyl APA 2e as a complexone is best
suitable for the sorption of actinides from nitric acid soluꢀ
tions.
Hence, we developed the simple and efficient method
for the synthesis of Nꢀalkylcarbamoylmethyl(dipheꢀ
nyl)phosphine oxides by amidation of ethyl diphenylꢀ
phosphorylacetate. The compounds obtained are efficient

2506
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004
Artyushin et al.
given in Table 1. The parameters of the 1H and 31P NMR and IR
extractants for extraction of actinides from nitric acid
solutions; APA with an unbranched substituent at the
N atom are more efficient than their branched analogs.
The compounds obtained can be used to prepare comꢀ
plexoneꢀbearing sorbents (solid extractants) for extracꢀ
tion of uranium(VI) from nitric acid solutions. The most
efficient sorbent was prepared by physisorption of
Nꢀnꢀoctylcarbamoylmethyl(diphenyl)phosphine oxide at
a XADꢀ7TM matrix.
spectra are presented in Table 2. 13C NMR (CDCl3), δ: 32.45
1
(NH2CH2CH2); 37.07 (NH2CH2); 38.50 (d, PCH2, JP,C
=
60.0 Hz); 39.00 (NHCH2); 128.63 (d, mꢀC, Ph, 3JP,C = 12.4 Hz);
130.50 (d, oꢀC, Ph, JP,C = 9.6 Hz); 131.34 (d, ipsoꢀC, C6H5P,
1JP,C = 102.8 Hz); 132.17 (d, pꢀC, Ph, JP,C = 2.8 Hz); 164.49
2
4
(NHC(O), 2JP,C = 4.4 Hz).
1,3ꢀBis(diphenylphosphorylacetylamino)propane (4b). A mixꢀ
ture of ester 1a (0.576 g, 2 mmol) and 1,3ꢀdiaminopropane
(0.74 g, 1 mmol) in 10 mL of anhydrous benzene was stored
at 20 °C until compound 1a was consumed (monitoring by
31P NMR). The solvent was removed in vacuo and the residue
was recrystallized three times from ethyl acetate, C6H6, and
C6H6/CCl4 in succession. The yield of the target bisamide 4b
was 0.42 g (38%). The physicochemical constants and elemental
analysis data are given in Table 1. The parameters of the 1H and
Experimental
NMR spectra were recorded on Bruker WPꢀ200SY and
Bruker AMXꢀ400 instruments in CDCl3 and DMFꢀd7 with reꢀ
sidual protons of the deuterated solvent as the internal standard
(1H, 13C) and to 85% H3PO4 as the external standard (31P).
13C NMR spectra were recorded in the JMODECHO regime;
signals for the C atoms bearing even and odd numbers of protons
are of opposite polarity. IR spectra were recorded on a Maꢀ
31P NMR and IR spectra are presented in Table 2. 13C NMR
1
(CDCl3), δ: 27.85 (NH2CH2CH2); 38.74 (d, PCH2, JP,C
=
60.2 Hz); 39.50 (NHCH2); 128.52 (d, mꢀC, Ph, 3JP,C = 12.4 Hz);
130.59 (d, oꢀC, Ph, JP,C = 9.7 Hz); 131.80 (d, ipsoꢀC, C6H5P,
1JP,C = 103.2 Hz); 132.92 (d, pꢀC, Ph, JP,C = 2.8 Hz); 164.26
2
4
(NHC(O), 2JP,C = 6.4 Hz).
gnaꢀIR 750 FTIRꢀspectrometer (Nicolet Co., resolution 2 cm–1
scan number 128, KBr pellets).
,
Bis(diphenylphosphorylacetylamino)alkanes (4a,c). A mixture
of ester 1a (0.576 g, 2 mmol) and an alkylenediamine (1 mmol)
in 3 mL of anhydrous ethanol was heated in a sealed tube in a
boiling water bath until compound 1a was consumed (monitorꢀ
ing by the 31P NMR method). The tube was opened, the solvent
was removed in vacuo, and the residue was recrystallized
from DMF. The recrystallized product was additionally washed
with water (5 mL) and EtOH (5 mL). The yields, physicochemiꢀ
cal constants, and elemental analysis data are given in Table 1.
The parameters of the 1H and 31P NMR and IR spectra are
presented in Table 2.
The starting phosphorylacetates 1a,b were prepared accordꢀ
ing to a standard procedure by the Arbuzov rearrangement of
ethyl esters of PIII acids with ethyl bromoacetate; the physicoꢀ
chemical constants of compounds 1a,b agreed with the literaꢀ
ture data.22
Ethyl 2ꢀethylhexyloxy(phenyl)phosphorylacetate (1c) was preꢀ
pared by analogy with compounds 1a,b from bis(2ꢀethylhexyl)
phenylphosphonite and ethyl bromoacetate and purified by chroꢀ
matography on silica gel (SiO2 100/160 mesh, Aldrich) in hexꢀ
ane—acetone with a gradient from 100 : 1 to 100 : 30. The yield
of compound 1c was 85%, heavy oil. Found (%): C, 63.43;
H, 8.37; P, 8.93. C18H29O4P. Calculated (%): C, 63.51; H, 8.59;
This work was financially supported by the Russian
Foundation for Basic Research (Project Nos. 02ꢀ03ꢀ33073
and 02ꢀ03ꢀ33111), the Foundation of the President of the
Russian Federation (Program for Support of Leading Sciꢀ
entific Schools of Russia, Grants NShꢀ1100.2003.3 and
NShꢀ1693.2003.3), the Russian Academy of Sciences
(Program of the Presidium of the Russian Academy of
Sciences, State Contract No. 10002ꢀ251/Pꢀ09/118ꢀ125/
250504ꢀ323), and the Foundation for Assistance to Doꢀ
mestic Science.
1
P, 9.10. 31P NMR (CDCl3), δ: 34.09. H NMR (CDCl3), δ:
0.81—0.87 (m, 6 H, Me); 1.13 (t, 3 H, C(O)OCH2CH3,
3JH,H
=
8.2
Hz);
1.20—1.45
(m,
8
H,
nꢀCH3(CH2)3CH(CH2CH3)CH2O—); 1.53—1.58 (m, 1 H,
nꢀCH3(CH2)3CH(CH2CH3)CH2O); 3.11 (dq, 2 H, PCH2,
2JP,H = 18.0 Hz and 2JH,H = 17.5 Hz); 3.82—3.74 and 3.96—4.02
3
(both m, 2 H each, POCH2); 4.05 (q, 2 H, C(O)CH2, JH,H
=
8.2 Hz); 7.44—7.84 (m, 5 H, C6H5P).
NꢀAlkylphosphorylacetamides 2a—n (general procedure).
A mixture of compound 1a,c (2 mmol) and a primary amine
(3 mmol) in 10 mL of anhydrous EtOH was heated in a sealed
tube in a boiling water bath for 8 to 10 h. The tube was opened,
the solvent was removed in vacuo, and the residue was recrystalꢀ
lized (2a—k,m,n) or purified by column chromatography on
silica gel (2l) in hexane—acetone with a gradient from 100 : 1 to
100 : 30 followed by crystallization while triturating it with hexꢀ
ane. The yields, physicochemical constants, and elemental analyꢀ
sis data are given in Table 1. The parameters of the 1H and
31P NMR and IR spectra are presented in Table 2.
Nꢀ(3ꢀAminopropyl)diphenylphosphorylacetamide (3b). A mixꢀ
ture of ester 1a (0.576 g, 2 mmol) and 1,3ꢀdiaminopropane
(0.128 g, 2 mmol) in 10 mL of anhydrous ethanol was stored
at 20 °C until compound 1a was consumed (monitoring by
31P NMR). The solvent was removed in vacuo and the residue
was recrystallized from benzene to give amide 3b (0.49 g, 77%).
The physicochemical constants and elemental analysis data are
References
1. T. Ya. Medved´, M. K. Chmutova, N. P. Nesterova, O. E.
Koiro, N. E. Kochetkova, B. F. Myasoedov, and M. I.
Kabachnik, Izv. Akad. Nauk SSSR, Ser. Khim., 1981, 2121
[Bull. Acad. Sci. USSR, Div. Chem. Sci., 1981, 30 (Engl.
Transl.)].
2. E. P. Horwitz, D. G. Kalina, H. Diamond, D. G. Vandergrift,
and W. W. Schultz, Solvent Extr. Ion. Exch., 1985, 3, 75.
3. E. P. Horwitz and W. W. Schultz, in Metal Ion Separation
and Preconcentration: Progress and Opportunities, Ch. XX,
Eds A. H. Bond, M. L. Dietz, and R. D. Rogers; Am. Nucl.
Soc., 1998.
4. V. N. Romanovskiy, I. V. Smirnov, A. Y. Shadrin, and B. F.
Myasoedov, Spectrum'98, Proc. Int. Topical Meeting: Nuclear

Synthesis of Nꢀalkylphosphorylacetamides
Russ.Chem.Bull., Int.Ed., Vol. 53, No. 11, November, 2004 2507
and Hazardous Waste Management, La Grange Park, Illinois;
Am. Nucl. Soc., 1998, 576.
Myasoedov, Abstrs XVII Mendeleev Conf. on General and
Applied Chemistry, Kazan, September, 21—26, 2003, p. 94.
13. K. M. Kem, N. V. Nguyen, and D. J. Gross, J. Org. Chem.,
1981, 25, 5188.
14. P. Amrhein, A. Shivanyuk, D. W. Johnson, and J. Rebek,
J. Am. Chem. Soc., 2002, 124, 10349.
15. S. E. Matthews, P. Parzuchowski, A. GarciaꢀCarrera,
C. Grüttner, J. F. Dozol, and V. Böhmer, Chem. Commun.,
2001, 417.
5. E. P. Horwitz, R. Chiarizia, M. L. Dietz, H. Diamond, and
D. M. Nelson, Anal. Chim. Acta, 1993, 281, 361.
6. E. P. Horwitz, M. L. Dietz, R. Chiarizia, H. Diamond,
A. M. Essling, and D. Grachyk, Anal. Chim. Acta, 1992,
266, 25.
7. J. Mellado, M. Llaerado, and G. Rawet, Anal. Chim. Acta,
2002, 458, 367.
8. G. I. Malofeeva, M. K. Chmutova, L. S. Rozhkova, O. M.
Petrukhin, B. Ya. Spivakov, and B. F. Myasoedov,
Radiokhimiya, 1998, 40, 235.
9. F. ArnaudꢀNeu, V. Böhmer, J.ꢀF. Dozol, C. Grüttner, R. A.
Jakobi, D. Kraft, O. Mauprivez, H. Rouquette, M.ꢀJ.
SchwingꢀWeill, N. Simon, and W. Vogt, J. Chem. Soc., Perkin
Trans. 2, 1996, 1175.
16. K. M. Yatsimirskii, M. I. Kabachnik, T. Ya. Medved´, N. P.
Nesterova, E. I. Sinyavskaya, L. V. Tsymbal, and F. I.
Bel´skii, Izv. Akad. Nauk SSSR, Ser. Khim., 1988, 53 [Bull.
Acad. Sci. USSR, Div. Chem. Sci., 1988, 37 (Engl. Transl.)].
17. M. K. Chmutova, M. N. Litvina, G. A. Pribylova, N. P.
Nesterova, V. E. Klimenko, and B. F. Myasoedov,
Radiokhimiya, 1995, 37, 430.
10. M. W. Peters, E. J. Werner, and M. J. Scott, Inorg. Chem.,
2002, 41, 1707.
18. M. N. Litvina, M. K. Chmutova, N. P. Nesterova, and B. F.
Myasoedov, Radiokhimiya, 1994, 36, 325.
11. R. Bernard, D. Cornu, B. Grüner, J.ꢀF. Dozol, P. Miele,
and B. Bonnetot, J. Organomet. Chem., 2002, 657, 83.
12. (a) V. P. Morgalyuk, G. A. Pribylova, D. E. Drozhko, L. A.
Ivanova, R. M. Kalyanova, O. I. Artyushin, M. V. Logunov,
I. G. Tananaev, T. A. Mastryukova, and B. F. Myasoedov,
Radiokhimiya, 2004, 46, 128; (b) M. K. Chmutova, L. A.
Ivanova, M. N. Litvina, O. I. Artyushin, D. E. Drozhko,
I. G. Tananaev, R. M. Kalyanova, N. A. Pavlova, T. A.
Mastryukova, A. D. Kuntsevich, and B. F. Myasoedov,
Radiokhimiya, 2002, 240; V. P. Morgalyuk, O. I. Artyushin,
R. M. Kalyanova, E. V. Sharova, I. G. Tananaev, D. E.
Drozhko, G. V. Myasoedova, T. A. Mastryukova, and B. F.
19. A. M. Rozen and B. V. Krupnov, Usp. Khim., 1996, 65, 1052
[Russ. Chem. Rev., 1996, 65 (Engl. Transl.)].
20. N. Kabay, V. Demircioplu, H. Ekinci, M. Yüsel, M. Saplam,
and M. Streat, React. Func. Polym., 1998, 38, 219.
21. E. P. Horwitz, M. L. Dietz, D. M. Nelson, J. J. LaRosa, and
W. D. Fairmann, Anal. Chim. Acta, 1990, 238, 263.
22. E. S. Petrov, E. N. Tsvetkov, M. I. Terekhova, R. A.
Malevannaya, A. I. Shatenshtein, and M. I. Kabachnik, Izv.
Akad. Nauk SSSR, Ser. Khim., 1976, 534 [Bull. Acad. Sci.
USSR, Div. Chem. Sci., 1976, 25 (Engl. Transl.)].
Received July 29, 2004