Mono and bis[N-aryl(benzyl)]amides of phosphorylacetic acids. One-pot synthesis and extraction of actinides from nitric acid solutions

Article abstract of DOI:10.1007/s11172-006-0437-2

A one-pot synthetic route to phosphorylacetic acid N-aryl(alkylaryl)amides, including those containing two phosphorylmethylcarbamoyl moieties attached to the arene framework, has been developed. The method is based on reactions of amines with the correspo

Full text of DOI:10.1007/s11172-006-0437-2

1440
Russian Chemical Bulletin, International Edition, Vol. 55, No. 8, pp. 1440—1447, August, 2006
Monoꢀ and bis[Nꢀaryl(benzyl)]amides of phosphorylacetic acids.
Oneꢀpot synthesis and extraction of actinides
from nitric acid solutions
a
a
aꢀ
a
a
a
O. I. Artyushin, E. V. Sharova, I. L. Odinets, K. A. Lyssenko, D. G. Golovanov, T. A. Mastryukova,
b
b
b
G. A. Pribylova, I. G. Tananaev, and G. V. Myasoedova
aA. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences,
8 ul. Vavilova, 119991 Moscow, Russian Federation.
2
Fax: +7 (495) 135 5085. Eꢀmail: odinets@ineos.ac.ru
V. I. Vernadsky Institute of Geochemistry and Analytical Chemistry, Russian Academy of Sciences,
b
1
9 ul. Kosygina, 119991 Moscow, Russian Federation
A oneꢀpot synthetic route to phosphorylacetic acid Nꢀaryl(alkylaryl)amides, including
those containing two phosphorylmethylcarbamoyl moieties attached to the arene framework,
has been developed. The method is based on reactions of amines with the corresponding acid
chlorides generated in situ with the use of phosphorus trichloride as a mild chlorinating agent.
The compositions and structures of the compounds obtained and their extraction ability toꢀ
III
ward Am were determined. Suggestions were made about the compositions of the extracted
complexes with phosphorylacetic acid Nꢀaryl(alkylaryl)amides.
Key words: aromatic amines, phenylenediamines, xylylenediamines, phosphorylacetic acids,
phosphorylacetic acid amides, carbamoylmethylphosphine oxides, actinides, americium, exꢀ
traction.
Phosphorylacetic acid N,Nꢀdialkylamides, in particuꢀ
lar, derivatives containing the phosphine oxide moiety
carbamoylmethylphosphine oxides (CMPO)), are nowaꢀ
days widely used as extractants for the processing of liquid
that the substituent R in the alkoxy group at the phosphoꢀ
rus atom contains at least eight carbon atoms. Study of
extraction of transuranium ions from acidic media with
amides 1 showed that the latter compounds are as good as
N,Nꢀdialkylꢀsubstituted diphenyl(carbamoylmethyl)phosꢀ
phine oxides for extraction of americium from nitric acid
media, and the presence of the hydrogen atom at the
nitrogen atom of the amide group increases hydrophilicꢀ
ity of organophosphorus complexation agents and changes
(
radioactive wastes.1
—4
The application of these comꢀ
pounds makes it possible to concentrate actinides from
highly active saltꢀcontaining wastes in a wide concentraꢀ
tion range of nitric acid without their preliminary correcꢀ
tion. Neutral organophosphorus complexing agents are
well compatible with various solvents. Secondary phosꢀ
8
,9
the character of complexation compared to CMPO.
III
phorylacetic acid Nꢀalkylamides also proved to be effiꢀ
Unlike the latter, extraction of Am showed no proꢀ
nounced dependence of the distribution coefficient DAm
on the structure of the complexation agent.
cient extractants for lanthanide ions.5
—8
The synthesis
and the extraction properties of compounds containing
the NHC(O)CH P(O)Ph fragments attached to the upꢀ
The aboveꢀdescribed procedure for the preparation of
secondary amides 1 has the following limitations: diꢀ
rect amidation of aromatic and aliphaticꢀaromatic priꢀ
mary amines cannot be performed, i.e., carbamoylmethylꢀ
2
2
5
per rim of calix[4]ꢀ and calix[5]arenes, to the C ꢀsymꢀ
metric triphenoxymethane framework, or the carborane
fragment were documented.
3
6
7
8
Earlier, we have developed a simple procedure for the
phosphine oxides containing an aromatic or CH ꢀaryl
2
preparation of the simplest representatives of this class of
fragment at the nitrogen atom, as well as phosphinates, in
which the substituent in the alkoxy group at the phosphoꢀ
rus atom contains less than eight carbon atoms, cannot be
obtained.
The aim of the present study was to develop a new
facile procedure for the synthesis of phosphorylacetic acid
Nꢀaryl(alkylaryl)amides based on the single organophosꢀ
phorus substrate and commercially available amines and
compounds, viz., alkylamides Ph P(O)CH C(O)NHAlk
2
2
(
1) (CMPOꢀNH, where Alk is alkyl C —C ), based on
2 12
direct amidation of commercially available ethyl diꢀ
phenylphosphorylacetate with primary aliphatic amines
(
75—92% yields). An analogous approach can be used for
the synthesis of phenyl(alkoxy)phosphorylacetic acid
alkylamides Ph(RO)P(O)CH C(O)NHAlk with proviso
2
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1387—1394, August, 2006.
066ꢀ5285/06/5508ꢀ1440 © 2006 Springer Science+Business Media, Inc.
1

Phosphorylacetic acid arylamides
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
1441
Scheme 1
R = Ph (4a), CH Ph (4b), CH CH Ph (4c)
2
2
2
investigate the extraction properties of the resulting comꢀ
pounds.
cation to give the corresponding amides 4a,b in high yields.
The analogous reactions with oꢀ and mꢀphenyleneꢀ
diamines and pꢀ and mꢀxylylenediamines produced comꢀ
pounds 5—8, in which two diphenylphosphorylmethylꢀ
carbamoyl fragments are attached to different positions in
the arene moiety (Scheme 1).
It appeared that this reaction has a general character
and allows one to prepare not only the corresponding
phosphine oxides but also phosphinates 5b,c and 9a—c.
In this reaction, both aromatic and aliphatic amines can
be used (Scheme 2).
After recrystallization from acetonitrile, chloroform,
or (in the case of phosphinates 9a—c) hexane followed by
chromatographic purification, amides 4—9 were isolated
as white crystalline compounds. Recrystallization of
amide 5a containing orthoꢀarranged complexing groups
from MeCN afforded a stable solvate complex with one
solvent molecule (MeCN) and one water molecule (m.p.
Results and Discussion
It seemed reasonable to use the reactions of the corꢀ
responding acid chlorides with amines as the simplest
approach to the synthesis of phosphorylacetic acid
Nꢀaryl(benzyl)amides. This approach is widely used in
synthetic organic chemistry.1 Earlier, we have employed
the similar procedure for the preparation of Nꢀalkylꢀ and
Nꢀdialkylamides from phosphorylcycloalkanecarboxylic
acids with the use of thionyl chloride as the chlorinating
agent. Oxalyl chloride12 (C H , ~20 °C) and sulfuryl chloꢀ
0
11
6
6
1
3
ride (CH Cl , ~20 °C) were used for the synthesis of
2
2
monosubstituted phosphorylacetic acid chlorides. In the
latter study, this chlorinating system was demonstrated to
be efficient in preparing diethoxyphosphorylacetic acid
chloride in nearly quantitative yield.
However, our attempts to reproduce this procedure13
for chlorination of phosphorylacetic acids containing laꢀ
bile methylene hydrogens failed. The reactions with the
use of thionyl or sulfuryl chloride produced diphenylphosꢀ
phorylacetic acid chloride in a yield of at most 30—40%
in spite of mild reaction conditions.
When studying the model reaction of diphenylphosꢀ
phorylacetic acid 2a, we found that phosphorus trichloꢀ
ride is a milder and more efficient chlorinating agent for
the transformation of phosphorylacetic acids into the corꢀ
responding acid chlorides. The reaction with this agent
proceeds at 0 °C and is not accompanied by side proꢀ
cesses. Acid chloride 3a was used in the further reactions
with aniline and benzylamine without additional purifiꢀ
1
24—125 °C).* The structure of this complex was estabꢀ
lished by Xꢀray diffraction.
The compositions and structures of the reaction prodꢀ
ucts were confirmed by elemental analysis (Table 1) and
IR and NMR spectroscopy (Table 2). The IR spectra of
amides 4—9 (KBr pellets) show characteristic absorption
–
1
–1
bands at 1663—1700 cm (C=O) and 1167—1184 cm
P=O). Absorption of the NH group appears as a broad
(
–
1
band at 3188—3262 cm (NH stretching vibrations) and
–
1
bands at 1540—1556 cm (combined frequencies of NH
bending vibrations and C—N vibrations). The CH bendꢀ
2
ing vibrations are observed at 1436—1443 cm– , two
1
*
The solvent molecules can be removed from complex
5a•MeCN•H O upon prolonged keeping in vacuo at high temꢀ
2
perature (110 °C, 1 Torr, 12 h).

1442
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
Artyushin et al.
Scheme 2
R = Bun (9a), nꢀC H (9b), nꢀC H (9c)
6
13
8 17
closely spaced absorption bands being observed for the
compounds containing the N—Ar bond (4a, 5—c, and 6).
The IR spectra of the resulting Nꢀarylꢀ and Nꢀ(benꢀ
zyl)amides are similar to each other and are comparable
with the spectra of their Nꢀalkyl analogs.
The 31P NMR spectra show singlets at δ 28.02—37.58
for compounds 4a,b, 5a, and 6—8 and at δ 38.43—38.46
for compounds 5b,c and 9a—c,, i.e., these signals appear
in the regions characteristic of this type of environment of
1
the phosphorus atom. The H NMR spectra are consisꢀ
tent with the structures of the resulting compounds and
have, along with characteristic signals for the hydrogen
atoms in the substituents at the phosphorus atom and the
amide fragment, the characteristic doublet for the protons
8
Table 1. Yields, physicochemical constants, and elemental analysis data for the PhRP(O)CH C(O)NHR´ compounds
2
Comꢀ
pound
R
R´
Yield*
(%)
M.p./°C
(solvent)
Found
Calculated
Molecular
formula
(
%)
C
H
N
4
4
5
5
5
6
7
8
9
9
9
a
b
a
b
c
Ph
Ph
Ph
100 (68)
100 (65)
87 (54)
227—228
71.21
71.63
71.17
71.20
68.96
68.92
59.18
59.09
63.36
63.71
68.81
5.41
5.41
5.68
5.77
5.09
5.10
5.30
5.72
5.68
5.57
5.07
5.10
5.38
5.52
5.37
5.52
7.75
7.83
8.51
8.42
9.01
8.91
4.11
4.18
3.99
4.01
4.61
4.73
5.27
5.30
6.01
6.19
4.69
4.73
4.39
4.51
4.16
4.51
4.92
4.94
4.28
4.50
4.09
4.13
C20H18NO2P
C21H20NO2P
(
MeСN)
207
СН Ph
2
(
MeСN)
Ph
(oꢀС Н )NHC(O)CH P(O)Ph
239—240
MeСN)
194—195
MeСN)
217—218
EtOAc)
C34H30N O P
2 4
6
4
2
2
2
2
(
EtO
EtO
Ph
(oꢀС Н )NHC(O)CH P(O)Ph(OEt)
91 (68)
C26H N O P
30 2 6
6
4
2
(
(pꢀС Н )С(О)NH(pꢀС Н )OMe
100 (82)
100 (77)
C24H25N O P
2 5
6
4
6
4
(
(mꢀС Н )NHC(O)CH P(O)Ph
294—295
217—218
314—315
86—87
C34H30N O P
2 4
6
4
2
2
2
2
2
6
8.92
69.53
9.67
69.31
9.67
59.37
9.35
61.68
1.72
63.89
3.70
Ph СН (mꢀС Н )СН NHC(O)CH P(O)Ph 100 (84)
C36H N O P
34 2 4
2
6
4
2
2
2
6
Ph СН (pꢀС Н )СН NHC(O)CH P(O)Ph 100 (79)
C36H N O P
34 2 4
2
6
4
2
2
2
6
a
b
c
EtO
EtO
EtO
Bun
nꢀС Н
96 (58)
85 (50)
86 (42)
C14H22NO3P
C H NO P
5
74—75
6
13
17
16 26
3
6
nꢀС Н
84—85
C18H30NO3P
8
6
*
The yield according to the 31P NMR spectroscopic data of the reaction mixture; the yield of the isolated compound is given in
parentheses.

Phosphorylacetic acid arylamides
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
1443
Table 2. 31P and H NMR and IR spectroscopic data for compounds 4—9
1
Comꢀ
pound
NMR (CDCl , δ, J/Hz)
IR, ν/cm–1
3
31P
1Н
= 12.7); 7.00—7.04 (m, 1 H, H , NPh);
C=O CH2 P=O NH
2
4
4
5
5
5
a
b
a
b
c
*
30.58 3.51 (d, 2 H, PCH , J
1684 1443, 1184 3188,
2
P,H
p
7
7
9
.20—7.23 (m, 2 H, H , NPh); 7.53—7.57 (m, 2 H, H , NPh);
1439
3249
m
o
.45—7.49 (m, 6 H, H , H , PPh); 7.72—7.77 (m, 4 Н, H , PPh);
p
m
o
.70 (br.s, 1 H, NH)
2
3
29.81 3.35 (d, 2 H, PCH , J
= 12.8); 4.38 (d, 2 H, NCH Ph, J = 5.9);
H,H
1663 1438 1175 3252,
1556
2
P,H
2
7
7
7
.08—7.09 (m, 2 H, H , C H СH ); 7.18—7.20 (m, 3 H, H , H , C H СH );
m 6 5 2 o p 6 5 2
.44—7.48 (m, 4 H, H , РPh); 7.53—7.56 (m, 2 H, H , PPh);
m
p
.68—7.73 (m, 4 Н, H , PPh); 7.77 (br.s, 1 H, NH)
o
2
30.31 3.75 (d, 4 H, PCH , J
= 13.2); 7.10 (dd, 2 Н, СAr(4)Н, СAr(5)Н,
P,H
1700 1436, 1167 3192,
2
3
4
JH,H = 5.6, J
= 3.4); 7.31—7.41 (m, 8 H, H , РPh); 7.45—7.50
1456
1553
H,H
m
3
(
4
m, 4 H, H , PPh); 7.59 (dd, 2 Н, СAr(3)Н, СAr(6)Н, J
= 5.8,
p
H,H
JH,H = 3.6); 7.64—7.71 (m, 8 Н, H , PPh); 9.79 (br.s, 2 H, NH)
o
39.08, 1.19—1.25 (m, 3 Н, CH СН О); 3.26—3.47 (m, 4 H, PCH ); 3.97—4.11
1686 1428, 1210 3270—
3
2
2
3
9.22 (m, 4 Н, MeСН О); 6.87—6.91 (m, 1 Н, Ar); 7.13—7.21 (m, 2 Н, Ar);
1439
3152
(br),
1553
2
7
7
.44—7.51 (m, 4 H, H , РPh); 7.54—7.59 (m, 2 H, H , PPh);
m p
.69 (br.s, 1 Н, Ar); 7.81—7.86 (m, 4 Н, H , PPh); 10.07 (br.s, 2 H, NH)
o
3
36.55 1.32 (t, 3 H, Me, J
= 7.0); 3.19—3.37 (m, 2 H, PCH ); 3.80 (s, 3 Н,
1680 1439 1210 3260
H,H
2
ОMe); 3.97—4.03, 4.10—4.18 (both m, 1 H each, MeСН О); 6.88 (d, 2 Н, Ar,
JH,H = 9.0); 7.48—7.52, 7.58—7.63 (both m, 9 Н, H , H , PPh, Ar);
2
3
p
m
7
.78—7.83 (m, 2 H, H , Ph, Ar); 8.14, 10.03 (both br.s, 1 H each, NH)
p
2
6
7
28.19 3.76 (d, 4 H, PCH , J
= 14.2); 7.17—7.18 (m, 3 Н, СAr(2)Н, СAr(4)Н,
1685 1437, 1174 1554
1430
2
P,H
СAr(6)Н); 7.51—7.58 (m, 12 H, H , H , PPh); 7.79—7.85 (m, 9 H, H , PPh,
o
p
m
СAr(5)Н); 10.14 (s, 2 H, NH)
2
29.94 3.38 (d, 4 H, PCH , J
= 12.7); 4.30 (d, 4 H, NНCH (mꢀС Н )СН NH,
1665 1437 1179 3262,
1540
2
P,H
2
6
4
2
3
3
JH,H = 6.0); 6.93 (d, 2 Н, СAr(4)Н, С (6)Н, J
Н, СAr(2)Н); 7.05 (t, 1 Н, СAr(5)Н, J
= 7.2); 7.00 (br.s,
H,H
Ar
3
1
= 7.3); 7.42—7.47 (m, 8 H,
H,H
H , РPh); 7.52—7.56 (m, 4 H, H , PPh); 7.67—7.72 (m, 8 Н, H , PPh);
m
p
o
7
.77 (br.s, 2 H, NH)
2
8
9
*
28.02 3.61 (d, 4 H, PCH , J
= 14.2); 4.18 (d, 4 H, NНCH (pꢀС Н )СН NH,
1667 1438 1179 3262,
1552
2
P,H
2
6
4
2
3
JH,H = 5.0); 6.99—7.13 (m, 3 Н, СAr(3)Н, СAr(5)Н, СAr(6)Нr); 7.52—7.57
m, 13 Н, H , H , PPh, С (2)Н); 7.79—7.84 (m, 8 Н, H , PPh);
(
o
p
Ar
m
8
.42 (br.s, 2 H, NH)
3
a
38.46 0.90 (t, 3 H, Me, J
= 7.5); 1.29—1.31 (m, 3 Н, MeСН О); 1.32—1.37
1661 1439 1206 3295,
1541
H,H
2
(
m, 2 H, NHCH CH CH Me); 1.43—1.50 (m, 2 H, NHCH CH CH Me);
2 2 2 2 2 2
3
2
4
.90—3.07 (m, 2 H, PCH ); 3.23 (q, 2 H, NCH , J
.07—4.14 (both m, 1 H each, MeСН О); 7.06 (br.s, 1 H, NH); 7.47—7.57
= 6.5); 3.94—3.98,
2
2
H,H
2
(
m, 3 H, H , H , PPh); 7.75—7.82 (m, 2 Н, H , PPh)
1662 1439 1205 3296,
1540
p
m
o
3
9
9
b
c
38.43 0.85 (t, 3,H, Me, J
= 6.4); 1.23—1.34 (m, 9 H, CH СН О,
H,H 3 2
NHCH CH (CH ) Me); 1.41—1.47 (m, 2 H, NHCH CH ); 2.88—3.05
2
2
2 3
2
2
3
(
(
m, 2 H, PCH ); 3.20 (q, 2 H, NCH , J
= 6.8); 3.89—3.96, 4.04—4.12
H,H
2
2
both m, 1 H each, MeСН О); 7.03 (br.s, 1 H, NH); 7.45—7.61 (m, 3 H,
2
H , H , PPh); 7.73—7.81 (m, 2 Н, H , PPh)
p
m
o
3
38.43 0.86 (t, 3 H, Me, J
= 6.5); 1.25—1.32 (m, 13 H, CH СН О,
1661 1439 1228, 3290,
1204 1540
H,H
3
2
NHCH CH (CH ) Me); 1.44—1.48 (m, 2 H, NHCH CH ); 2.88—3.06
2
2
2 5
2
2
3
(
(
m, 2 H, PCH ); 3.21 (q, 2 H, NCH , J
= 6.6); 3.91—3.97, 4.07—4.13
H,H
2
2
both m, 1 H each, MeСН О); 7.00 (br.s, 1 H, NH); 7.48—7.58 (m, 3 H,
2
H , H , PPh); 7.72—7.83 (m, 2 Н, H , PPh)
p
m
o
The H and 31P NMR spectra were recorded in DMSOꢀd6.
1
*
of the PCH group at δ 3.35—3.75 with the coupling
To obtain additional data on the resulting neutral
ligands, the molecular structures of diphenylphosphorylꢀ
acetic acid phenylamide 4a and the solvate of comꢀ
pound 5a, in which two carbamoylmethylphosphoryl fragꢀ
ments are in the ortho positions of the benzene ring, were
2
constant of 12.7—14.2 Hz for phosphine oxides 4a,b, 5a,
and 6—8. In the spectra of phosphinates 5b,c and 9a—c
containing the asymmetric phosphorus atom, this signal
appears as an ABX system at δ 2.88—3.07.

1444
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
Artyushin et al.
C(18)
C(17)
The introduction of the second phosphorusꢀcontainꢀ
ing group has no effect on the bond lengths in the
carbamoylmethylphosphoryl fragments of compounds 4a
and 5a (see Table 3). Moreover, a comparison of the
mutual arrangement of the amide substituents in amides
C(19)
C(16)
C(15)
C(20)
4
a and 5a indicates that the introduction of the secꢀ
ond complexing fragment and the presence of the solꢀ
vent water molecule do not lead to the change in the
C(2)—C(1)—N(1)—C(7) torsion angle (in both strucꢀ
tures, this angle is 171.1°). The observed stability of the
antiperiplanar conformation of the C(2)C(1)N(1)C(2)
fragment is evidently attributed to conjugation of the
amide group with the aromatic ring. To the contrary, the
amide group at the C(2) atom in molecule 5a is anticlinal
P(1)
O(1)
C(9)
C(8)
C(7)
C(14)
C(13)
C(12)
H(1N)
N(1)
C(10)
C(11)
(
C(1)—C(2)—N(1´)—C(7´) torsion angle is 115.1°), due
C(2)
apparently to steric repulsion between the amide groups.
The conformation of the phosphorylmethylcarbamoyl
groups in molecules 4a and 5a also changes only slightly.
In both compounds, the O(1)—P(1)—C(8)—C(7) and
P(1)—C(8)—C(7)—N(1) torsion angles for the substituꢀ
ent at the C(1) atom are virtually equal (63.2, 99.8°
and 62.9, 100° for 4a and 5a, respectively). The analogous
parameters for the substituent at the C(2) atom in 5a are
O(2)
C(1)
C(3)
C(6)
C(5)
C(4)
Fig. 1. General view of molecule 4a.
4
6.6 and 81.9°, respectively.
The solvent water molecule in the crystal structure of
established by Xꢀray diffraction. The general views of these
compounds are shown in Figs 1 and 2, respectively. Seꢀ
lected bond lengths and bond angles are given in Table 3.
5a is located between two substituents and is held by the
N(1´)—H(1N´)...O(1W) (N(1´)...O(1W), 2.865(3) Å) and
O(1W)—H(1WB)...O(1) (O(1W)...O(1), 2.898(2) Å)
C(18´)
C(17´)
C(19´)
C(18)
C(17)
C(16´)
C(20´)
C(19)
C(20)
C(16)
C(15)
O(1)
C(15´)
H(1WA)
O(1W)
O(1´)
P(1)
P(1´)
C(14´)
C(13´)
C(14)
H(1WB)
C(9´)
C(13)
C(12)
C(8´)
H(1N´)
C(7´)
C(9)
C(8)
C(12´)
C(11´)
O(2´)
C(10)
H(1N)
C(10´)
C(11)
C(7)
N(1´)
C(2)
C(3)
N(1)
C(1)
O(2)
C(6)
C(4)
C(5)
Fig. 2. General view of molecule 5a•MeCN•H O.
2

Phosphorylacetic acid arylamides
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
1445
Table 3. Selected bond lengths (d) and bond angles (ω) in molecules 4a and 5a
Parameter
4а
Parameter
5а
Parameter
5а
Bond
d/Å
Bond
d/Å
Bond
d/Å
P(1)—O(1)
P(1)—C(8)
P(1)—C(9)
P(1)—C(15)
O(2)—C(7)
N(1)—C(7)
N(1)—C(1)
C(1)—C(2)
1.494(3)
1.805(3)
1.796(3)
1.812(4)
1.221(4)
1.353(4)
1.415(4)
1.392(5)
ω/deg
P(1´)—O(2´)
P(1´)—C(8´)
P(1´)—C(9´)
P(1´)—C(15´)
O(1´)—C(7´)
N(1)—C(7)
N(1)—C(1)
C(1)—C(2)
Angle
1.492(2)
1.810(3)
1.797(3)
1.798(3)
1.213(3)
1.356(4)
1.412(4)
1.415(4)
ω/deg
P(1)—O(2)
P(1)—C(8)
P(1)—C(9)
P(1)—C(15)
O(1)—C(7)
N(1´)—C(7´)
N(1´)—C(2)
1.497(2)
1.804(3)
1.803(3)
1.788(3)
1.225(3)
1.365(4)
1.420(4)
Angle
Angle
ω/deg
O(1)—P(1)—C(9)
O(1)—P(1)—C(8)
C(9)—P(1)—C(8)
O(1)—P(1)—C(15)
C(9)—P(1)—C(15)
C(8)—P(1)—C(15)
C(7)—N(1)—C(1)
C(2)—C(1)—C(6)
C(3)—C(2)—C(1)
113.0(1)
111.3(2)
106.6(1)
112.9(1)
108.3(2)
104.1(2)
127.6(3)
119.2(3)
120.1(4)
O(1´)—P(1´)—C(15´) 113.3(1)
O(1´)—P(1´)—C(9´) 110.3(1)
C(15´)—P(1´)—C(9´) 108.0(1)
O(1´)—P(1´)—C(8´) 111.7(1)
C(15´)—P(1´)—C(8´) 105.2(1)
O(1)—P(1)—C(15)
O(1)—P(1)—C(9)
C(15)—P(1)—C(9)
O(1)—P(1)—C(8)
C(15)—P(1)—C(8)
C(9)—P(1)—C(8)
C(7)—N(1)—C(1)
111.9(1)
111.3(1)
109.1(1)
112.3(1)
104.0(1)
107.8(1)
127.7(3)
C(9´)—P(1´)—C(8´)
C(7´)—N(1´)—C(2)
C(6)—C(1)—C(2)
C(3)—C(2)—C(1)
108.05(1)
122.4(3)
118.5(3)
120.1(3)
hydrogen bonds. In addition to these hydrogen bonds,
there are also hydrogen bonds through which molecules
2.803(2) Å) due to which phenylamide molecules 4a are
linked to each other to form chains along the crystalloꢀ
graphic axis c. Therefore, in the case of competitive hyꢀ
drogen bonding in the crystals of 4a and 5a, the hydrogen
bonds with the phosphoryl groups are more favorable than
those with the carbonyl groups.
5
a in the crystal structure are linked to each other to form
dimers, viz., the intramolecular N(1)—H(1N)...O(1´)
hydrogen bond (N(1)...O(1´), 2.929(3) Å) and the inꢀ
termolecular O(1W)—H(1WA)...O(1) hydrogen bond
(
1 – x, –y, –z) (O(1W)...O(1), 2.801(3) Å). The solvent
Study of the extraction ability of Nꢀphosphorylacetic
acid aryl(arylalkyl)amides of the general formula
Ph P(O)CH C(O)NHR (R = Ph (4a), CH Ph (4b), and
acetonitrile molecule is located between the Hꢀbonded
dimers and is not involved in strong intermolecular interꢀ
actions.
2
2
2
III
CH CH Ph (4c)) toward Am demonstrated that comꢀ
2
2
In the crystal structures of both 4a and 5a, there are
intermolecular bonds between the amide and phosphoryl
groups (N(1)—H(1N)...O(1) (x, 1 – y, х + z), N(1)...O(1),
plexes extracted by these ligands from 3 M HNO soluꢀ
3
tions into an organic phase differ in composition. This
fact is illustrated by the logarithmic dependence of the
III
distribution coefficients of Am (logDAm) on the conꢀ
logDAm
centration of the complexing agent in chloroform (log[L])
shown in Fig. 3. For example, in the concentration range
from 0.01 to 0.08 mol L , compounds 4a and 4b conꢀ
–
–
–
–
1.5
2.0
2.5
3.0
–
1
taining the phenyl and benzyl substituents at the nitrogen
III
III
atom extract Am as 1 : 1 complexes,* whereas Am is
extracted as a 1 : 2 complex by amide 4c. According to the
data on extraction of trivalent actinides, the compositions
of the complexes extracted by carbamoylmethylphosꢀ
1
4
phoryl compounds are generally 1 : 2 or 1 : 3. Presumꢀ
ably, the formation of 1 : 1 Am complexes with ligands
2
III
4
a and 4b is attributed to steric hindrances due to the
1
3
presence of the bulky Ph and CH Ph substituents, respecꢀ
2
tively, adjacent to the coordinated carbonyl group, thus
III
hindering binding of the second ligand molecule to Am
.
–
2.0
–1.8
–1.6
–1.4
–1.2
log[L]
A decrease in steric hindrance in amide 4c leads to formaꢀ
Fig. 3. Plots of the distribution coefficients of AmIII for extracꢀ
tion from 3 M HNO vs. the concentration of the ligands conꢀ
taining different substituents at the nitrogen atom of the carꢀ
bamoyl group in chloroform: 4a (1), 4b (2), and 4c (3).
* A further increase in the concentration of 4a and 4b to
0.1 mol L– leads apparently to extraction of complexes of comꢀ
positions 1 : 2 (4a) and 1 : 3 (4b).
3
1

1
446
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
Artyushin et al.
tion of a complex of standard composition. The extracꢀ
tion ability of the AmIII complexes with the ligands under
the solvent was removed in vacuo, and the residue was purified
by recrystallization and dried in vacuo over P O5 to constant
2
weight. In the case of compounds 6 and 8, which are virtually
insoluble in CHCl3, the organic layer was filtered after washing
with water. The resulting crystals were washed with several porꢀ
study differs only slightly. For example, logD
traction of Am by 0.05 M solutions of 4a, 4b, and 4c in
for exꢀ
Am
III
chloroform is –2.22, –2.07, and –2.38, respectively. The
tions of CHCl and dried in vacuo over P O to constant weight.
III
3
2
5
experimental data on extraction of Am show that the
The yields, physicochemical characteristics, elemental analysis
extraction ability of carbamoylmethylphosphine oxides
containing an Nꢀaryl or Nꢀalkylaryl fragment is lower
than that of analogs containing N,Nꢀdialkyl or Nꢀalkyl
1
31
data, and spectroscopic parameters ( H and P NMR and IR)
of the resulting compounds are given in Tables 1 and 2. The
physicochemical characteristics of diphenylphosphorylacetic
acid Nꢀphenylethylamide 4c synthesized according to this proꢀ
cedure are identical to those for compound 4c prepared by diꢀ
rect amidation of ethyl diphenylacetate with phenylethylamine
according to a procedure described earlier.8
8,15
substituents studied earlier.
steric hindrances and the electronic properties of the
(CH ) Ph groups, which decrease the basicity and, as a
Apparently, this arises from
—
2
n
consequence, the complexation and extraction properties
of phosphorylacetic acid amides.16
Table 4. Principal crystallographic data and details of structure
refinement for compounds 4a and 5a
To conclude, we developed a oneꢀpot synthetic route
to phosphorylacetic acid Nꢀaryl(alkylaryl)amides based
on the reactions of the corresponding amines and phosꢀ
phorylacetic chlorides synthesized in situ with the use of
phosphorus trichloride as a mild chlorinating agent. The
obvious advantage of the aboveꢀdescribed procedure for
the synthesis of alkylamides CMPOꢀNH over direct
Parameter
4а
5а
Molecular formula
C20H NO P C34H30N O P •
18
2
2
4 2
•H O•MeCN
2
Diffractometer
Radiation
Scanning technique
T/K
«Syntex P21»
MoꢀKα
θ/2θ
«Smart CCD»
8
MoꢀKα
ω
120
amidation of ethyl phosphorylacetates is the absence of
limitations on the nature of amine or substituents at the
phosphorus atom. The ability of phosphorylacetic acid
173
Crystal system
Space group
a/Å
b/Å
c/Å
Monoclinic
Сс
19.347(6)
11.711(3)
8.102(1)
—
111.68(1)
—
1706.0(7)
4 (1)
Triclinic
III
Nꢀaryl(alkylaryl)amides to form complexes with Am
–
P1
was examined by the extraction method. It was demonꢀ
strated that complexes of different composition are exꢀ
tracted into an organic phase depending on the length of
the alkylene fragment between the nitrogen atom and the
phenyl group.
8.795(2)
12.832(2)
15.008(3)
77.446(4)
84.892(5)
76.414(5)
1605.9(5)
2 (1)
α/deg
β/deg
γ/deg
3
V/Å
Experimental
Z (Z´)
M
µ/cm
F(000)
ρcalc/g cm–3
2θmax/deg
Number of measured
reflections (Rint
Number of independent
reflections
335.32
1.73
704
1.306
50
1551
(0.0*)
1551
651.61
1.84
684
1.348
56
14146
(0.0580)
7713
The 1H and 31P NMR spectra were recorded on Bruker
AMXꢀ400 (400.13 and 161.98 MHz, respectively) and Bruker
AVꢀ300 (300.09 and 121.49 MHz, respectively) instruments in
CDCl and DMSOꢀd with the use of the signal of the residual
–1
3
6
1
protons of the deuterated solvent as the internal standard ( H)
31
and 85% H PO as the external standard ( P). The IR spectra
3
4
)
were measured on a MagnaꢀIR 750 Fourierꢀtransform specꢀ
trometer (Nicolet), the resolution 2 cm–1, the number of
scans 128 (KBr pellets).
Starting phosphorylacetic acids 2a17 and 2b18 were syntheꢀ
sized by hydrolysis of ethyl esters of the corresponding acids
according to a modified procedure.17 Their physicochemical
characteristics are identical to those published in the literature.
Phosphorylacetic acids Nꢀarylamides (general procedure).
Phosphorus trichloride (3.6 mmol) was added dropwise with
stirring and cooling to 0 °C to a solution of phosphorylacetic
Number of observed
reflections with I > 2σ(I )
Number of parameters
1371
3832
290
0.0335
443
0.0621
R (based on observed
1
reflections)
wR (based on
all reflections)
GOF
Residual electron
0.0840
0.1364
2
0.994
0.262/–0.291
0.973
0.582/–0.362
acid (9 mmol) in anhydrous CHCl (20 mL). Then cooling was
3
stopped, and the mixture was stirred at 20 °C for 5 h and cooled
to 0 °C. A solution of triethylamine (10 mmol) and the correꢀ
sponding amine (9 mmol) or diamine (4.5 mmol) in anhydrous
–3
density/e Å
ρmax/ρmin
,
CHCl (20 mL) was slowly added dropwise. The reaction mixꢀ
* The value Rint = 0 is attribuited to the fact that the Friedel
pairs of zeroꢀlayer reflections were in the region of forbidden
χ angles due to the LT geometry of the attachement; the comꢀ
pleteness of the data set was 99.8%.
3
ture was stirred at 20 °C for 2 h and allowed to stand for ~14 h.
Then water (20 mL) was added, the organic layer was separated,
washed with water (50 mL), dried with Na SO , and filtered,
2
4

Phosphorylacetic acid arylamides
Russ.Chem.Bull., Int.Ed., Vol. 55, No. 8, August, 2006
1447
Xꢀray diffraction study of compounds 4a and 5a. Xꢀray difꢀ
fraction data sets for compounds 4a and 5a were collected on a
4. V. N. Romanovskiy, I. V. Smirnov, A. Y. Shadrin, and B. F.
Myasoedov, Spectrum´98, Proc. Int. Topic. Meet. Nuclear
and Hazardous Waste Management (La Grange Park, Illiꢀ
nois), Am. Nucl. Soc., La Grange Park, Illinois, 1998, 576.
5. F. ArnaudꢀNeu, V. Bëhmer, 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.
fourꢀcircle Syntex P2 diffractometer (MoꢀKα radiation, graphꢀ
1
ite monochromator, θ/2θ scanning technique) at 173 K and
a threeꢀcircle SMART CCD diffractometer (MoꢀKα radiation,
graphite monochromator, ωꢀscanning technique) at 120 K, reꢀ
spectively. Principal crystallographic characteristics and details
of structure refinement are given in Table 4. Semiempirical abꢀ
sorption corrections were applied based on equivalent reflecꢀ
tions. The structures were solved by direct methods and refined
6. M. W. Peters, E. J. Werner, and M. J. Scott, Inorg. Chem.,
2002, 41, 1707.
by the fullꢀmatrix leastꢀsquares method against F 2 with anisoꢀ
7. R. Bernard, D. Cornu, B. Grüner, J.ꢀF. Dozol, P. Miele,
and B. Bonnetot, J. Organometal. Chem., 2002, 657, 83.
8. O. I. Artyushin, E. V. Sharova, I. L. Odinets, S. V. Lenevich,
V. P. Morgalyuk, I. G. Tananaev, G. V. Pribylova, G. V.
Myasoedova, T. A. Mastryukova, and B. F. Myasoedov, Izv.
Akad. Nauk, Ser. Khim., 2004, 2395 [Russ. Chem. Bul., Int.
Ed., 2004, 53, 2499].
hkl
tropic displacement parameters for nonhydrogen atoms. The
hydrogen atoms were located in difference Fourier maps and
refined isotropically. All calculations were performed with the
use of the SHELXTL PLUS program package.1
9
Extraction was studied with the use of nitric acid solutions of
241AmIII
and nitric acid of special purity grade. Chloroform was
used for dilution. Solutions of the complexing agents in dichloroꢀ
ethane were prepared using precisely weighed samples.
The extraction with the complexing agents was studied
9. 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 [Radiochemistry, 2004, 46 (Engl.
Transl.)].
10. L. F. Tietze and T. Eicher, Reactionen und Synthesen im
OrganischꢀChemischen Praktikum und Forschungslaboraꢀ
torium, Georg Thieme Verlag, Stuttgart—New York, 1991
(and references therein).
11. I. L. Odinets, P. V. Kazakov, R. U. Amanov, M. Yu. Antipin,
L. V. Kovalenko, and T. A. Mastryukova, Izv. Akad. Nauk,
Ser. Khim., 1992, 1879 [Bull. Russ. Acad. Sci., Div. Chem.
Sci., 1992, 41, 1466 (Engl. Transl.)].
at 20±1 °C. Aliquots of 2 Am in 3 M nitric acid and a
complexing agent in chloroform were placed in test tubes with
ground stoppers. The phases were stirred for 3 min (this time was
sufficient to achieve the equilibrium). After separation of the
phases by centrifugation, the aliquots were withdrawn, and their
γ activity was determined followed by calculations of the distriꢀ
bution coefficients of the elements (D). The distribution coeffiꢀ
cients were determined as the ratio of the percentage of the
element in the organic phase to its percentage in the aqueous
phase.
41
III
1
2. J.ꢀF. Devaux, S. V. O´Neil, N. Guillo, and L. A. Paquette,
Collect. Czech. Chem. Commun., 2000, 65, 490.
This study was financially supported by the Russian
Foundation for Basic Research (Project Nos 05ꢀ03ꢀ33094
and 05ꢀ03ꢀ32692), the Council on Grants of the Presiꢀ
dent of the Russian Federation (Program for State Supꢀ
port of Leading Scientific Schools of the Russian Federaꢀ
tion, Grants NShꢀ1100.2003.3 and NShꢀ1693.2003.3),
and the Russian Science Support Foundation.
13. P. Coutrot and A. Ghribi, Synthesis, 1986, 661.
14. Y. M. Kulyako, D. A. Malikov, M. K. Chmutova, M. N.
Litvina, and B. F. Myasoedov, J. All. Comp., 1998, 760.
1
5. A. M. Rozen, A. S. Nikiforov, Z. I. Nikolotova, and N. A.
Kartashova, Atomnaya energiya [Atomic Energy], 1985, 59,
4
13 (in Russian); A. M. Rozen, V. I. Volk, A. Yu. Vakhrushin,
B. S. Zakharkin, N. A. Kartasheva, B. V. Krupnov, and Z. I.
Nikolotova, Radiokhimiya, 1999, 41, 205 [Radiochem., 1999,
41 (Engl. Transl.)].
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Received March 20, 2006;
in revised form June 27, 2006