One-pot method for the preparation of bis[N′-(diphenylphosphoryl) ureido]alkanes,-cycloalkanes, and -arenes

Full text of DOI:10.1134/S0012500808040022

ISSN 0012-5008, Doklady Chemistry, 2008, Vol. 419, Part 2, pp. 87–90. © Pleiades Publishing, Ltd., 2008.
Original Russian Text © E.I. Goryunov, T.V. Baulina, I.B. Goryunova, E.D. Savin, P.V. Petrovskii, E.I. Matrosov, E.E. Nifant’ev, 2008, published in Doklady Akademii Nauk, 2008,
Vol. 419, No. 4, pp. 504–507.
CHEMISTRY
One-Pot Method for the Preparation
of Bis[N'-(diphenylphosphoryl)ureido]alkanes,
-cycloalkanes, and -arenes
E. I. Goryunov, T. V. Baulina, I. B. Goryunova, E. D. Savin, P. V. Petrovskii,
E. I. Matrosov, and Corresponding Member of the RAS E. E. Nifant’ev
Received October 30, 2007
DOI: 10.1134/S0012500808040022
Processing of acid-containing liquid radioactive thyl)phosphine oxides, containing the methylene
waste (LRW) is one of the major problems of modern bridge instead of the imide fragment.
nuclear industry. LRW is very environmentally hazard-
The data obtained show that it is promising to search
ous due to the presence of long-lived radionuclides,
for efficient and selective extractants of radioactive
especially actinides and lanthanides [1]. Different
f elements from LRW among N-diphenylphosphoryl-
ureas (and related compounds).
methods for the removal of radioactive f elements from
LRW are known at present; however, the most promis-
A possible line of investigation is the design of poly-
ing method for solving this important practical problem
dentate compounds containing two N'-diphenylphos-
is liquid extraction with, first of all, bidentate neutral
phorylureido fragments linked by alkylene, cycloalkyl-
organophosphorus compounds.
ene, or arylene bridges. It should be noted that, inas-
In recent years, special attention has been paid to the
study of the possibility of using carbamoylmethylphos-
phine oxides of different structure as extractants for
actinides and lanthanides. Extraction technologies for
the isolation of actinides from LRW were developed on
the basis of diphenyl(N,N-dibutylcarbamoylme-
thyl)phosphine oxide [2] and octylphenyl(N,N-diisobu-
tylcarbamoylmethyl)phosphine oxide [3]. Unfortu-
nately, these compounds are insufficiently selective and
rather expensive owing to the complex methods of their
synthesis. In this context, the search for new efficient
but cheaper and substantially more selective bidentate
neutral organophosphorus extractants remains an
important task.
much as phosphorus-containing diureas of such a kind
1
have not been described in the literature thus far , a
high-priority task is to develop a simple and easily
implemented method for their preparation.
We have found that a three-stage one-pot process
based on commercially available chlorodiphenylphos-
2
phine as the initial organophosphorus compound can
serve as a general method for the synthesis of diureas
[Ph2P(O)NHC(O)NH]2Z (IIa–IIh) containing diphe-
nylphosphoryl substituents at both terminal nitrogen
atoms (see Scheme 1).
The first stage of this process is the oxidation of
chlorodiphenylphosphine with sulfuryl chloride in car-
bon tetrachloride at ambient temperature to give diphe-
nylphosphinic chloride in practically quantitative yield
(99.8% according to 31P NMR spectra). The latter com-
pound without additional purification was further
reacted with sodium cyanate in the presence of anhy-
drous magnesium chloride as a catalyst. This stage pro-
ceeds in an acetonitrile medium at ambient temperature
at a rather high rate and does not produce by-products,
so that the yield of diphenylphosphoryl isocyanate III
is about 98% according to 31P NMR spectra. This fea-
ture makes it possible to use the resulting isocyanate
Recently, we have established that N-diphenylphos-
phoryl-N'-alkylureas Ph2P(O)NHC(O)NHCnH2n + 1 (I,
n = 6–10) behave as efficient extractants capable of
extracting actinides and lanthanides from nitric acid
solutions with high distribution coefficients, including
in the presence of considerable amounts of salts of
other metals such as Fe(III), Ni(II), Cr(III), etc. [4, 5].
The efficiency and selectivity of phosphorus-con-
taining ureas I are substantially higher than those of
structurally related diphenyl(N-alkylcarbamoylme-
1
Only the preparation of diureas containing dialkoxyphosphoryl
fragments at the terminal nitrogen atoms was reported (see, e.g.,
[6, 7]).
Nesmeyanov Institute of Organoelement Compounds,
Russian Academy of Sciences, ul. Vavilova 28, Moscow,
119991 Russia
2
Previously, we used a similar process for the synthesis of
N-diphenylphosphorylated monoureas I [8].
87

88
GORYUNOV et al.
without isolation in the final, third stage of the one-pot hydrogen bonds with the oxygen atoms of C=O and
process. At this stage, a calculated amount of the appro- P=O fragments. It is likely that this fact causes a con-
priate diamine is added to a solution of isocyanate III siderable spread of ν P=O and ν C=O values observed
in acetonitrile at ambient temperature and ureas IIa– in the IR spectra of phosphorus-containing diureas
IIh are obtained after routine treatment.
IIa−IIh.
The 31ê{1H} NMR spectra of ureas IIa–IIg obtained
SO2Cl2, ≈20°C
Ph2PCl
[Ph2P(O)Cl]
CCl4
in dimethyl sulfoxide-d6 (IIa–IIf) or trifluoroacetic
acid-d (IIg) show singlet signals. The signals are
3
NaOCN, [MgCl2], ≈20°C
within 14–15 ppm for the dimethyl sulfoxide solution,
whereas a considerable downfield shift is observed in
trifluoroacetic acid (up to 33 ppm), which is likely to
result from the formation of a protonated form of the
[Ph2P(O)NCO]
MeCN
III
1. H2N–Z–NH2, ≈20°C; 2. H2O
[Ph2P(O)NHC(O)NH]2Z,
urea in a strongly acidic medium. The ê{1H} NMR
31
IIa–IIh
spectrum of urea IIh in dimethyl sulfoxide-d6 shows
two close singlet signals of equal intensity, which agree
well with the structure of this compound, containing
two chemically related but not identical phosphorus
atoms.
where Z is
a
–(CH2)3–
b
d
–(CH2)4–
Thus, we developed a simple and efficient one-pot
method for the synthesis of previously unknown diphe-
nylphosphorylated diureas. All stages of the process are
carried out at ambient temperature, there is no need to
isolate pure intermediate hydrolytically unstable com-
pounds, the target compounds obtained by this method
require no additional purification, and their yield is
close to quantitative.
c
CH2
e
f
CH2
EXPERIMENTAL
The 31ê{1H} NMR spectra of the compounds
obtained were recorded on Bruker AV-300 and Bruker
AV-400 spectrometers operating at 121.50 and
161.98 MHz, respectively. Solvents used were
(CD3)2SO and CF3COOD; 85% H3PO4 was used as an
external reference. IR spectra were recorded as KBr
pellets on a UR-20 spectrometer.
CH2
g
h
CH2
CH2
Scheme 1.
This one-pot process can involve different types of
symmetrical and unsymmetrical diamines as nitrogen
nucleophiles: alkylamines, cycloalkylamines, aryl-
amines, and aralkylamines. In all studied reactions, the
yield of diphosphorylated diureas II was higher than
90% (calculated in terms of initial chlorodiphenylphos-
phine) and their purity was at least 98%. The yields,
melting points, and elemental analysis data of the com-
pounds obtained are given in Table 1.
NaOCN (Aldrich) was dried for 4 h at 120°C in vac-
uum over P2O5; 1,3-propanediamine, 1,4-butanedi-
amine, trans-1,2-cyclohexanediamine, m-xylylenedi-
amine, and p-xylylenediamine (Acros and Aldrich)
were purified by distillation over solid KOH; o-phe-
nylenediamine (Acros) was recrystallized from a hep-
tane–chloroform
mixture;
m-phenylenediamine
The structure of phosphorus-containing diureas
IIa–IIh was confirmed by IR and 31P NMR spectra
(Table 2). The IR spectra of these compounds show the
absorption bands of C=O groups in the region 1650–
1710 cm–1 and the absorption bands of P=O groups in
the region 1175–1220 cm–1. The spectra of 1-[N'-
(diphenylphosphoryl)ureido]-3-[[N'-(diphenylphos-
phoryl)ureido]methyl]benzene IIh, where both carbo-
nyl groups and both phosphoryl groups are chemically
different, show a marked broadening of the absorption
bands of the corresponding groups. The IR spectra of
diureas IIa–IIh show a wide absorption band of NH
vibrations in the range 3050–3350 cm–1 with a series of
maxima, which is evidence of the participation of
amide groups in the formation of different types of
(Acros) was recrystallized from benzene; carbon tetra-
chloride and acetonitrile were distilled over P2O5 prior
to use. m-Aminobenzylamine was obtained by the
known procedure [9].
One-pot synthesis of bis(diphenylphosphory-
lated) diureas IIa–IIh. A solution of 2.7 g (0.02 mol)
of freshly distilled SO2Cl2 in 5 mL of freshly distilled
CCl4 was added dropwise under an argon atmosphere at
ambient temperature over 40 min to a magnetically
stirred solution of 3.64 g (0.0165 mol) of chlorodiphe-
3
The use of this deuterated solvent proved to be necessary on
account of a very poor solubility of the corresponding urea even
in such efficient solvents as dimethyl sulfoxide and dimethyl-
formamide.
DOKLADY CHEMISTRY Vol. 419 Part 2 2008

ONE-POT METHOD FOR THE PREPARATION
89
Table 1. Yields, melting points, and elemental analysis data for bis(diphenylphosphorylated) diureas [Ph2P(O)NHC(O)NH]2Z
IIa–IIh
Found/Calculated, %
Molecular
Compound Yield, %
Tm, °C
formula
C
H
N
P
61.87
------------
62.14
5.28
---------
5.39
9.94
---------
9.98
10.81
------------
11.05
IIa
IIb
IIc
IId
IIe
IIf
96.3
90.8
95.0
92.0
96.6
91.4
93.0
95.1
197–198
210–212
211.5–212
196–198
201–202
198–199
231–232
203–205
C29H30N4O4P2
C30H32N4O4P2
C32H34N4O4P2
C32H28N4O4P2
C32H28N4O4P2
C34H32N4O4P2
C34H32N4O4P2
C33H30N4O4P2
62.78
------------
62.71
5.58
---------
5.61
9.75
---------
9.75
10.73
------------
10.78
63.99
------------
63.99
5.85
---------
5.71
9.15
---------
9.33
9.98
------------
10.31
64.69
------------
64.65
4.78
---------
4.75
9.57
---------
9.43
10.40
------------
10.42
64.64
------------
64.65
4.68
---------
4.75
9.36
---------
9.43
9.98
------------
10.42
65.57
------------
65.59
5.21
---------
5.18
9.07
---------
9.00
9.73
---------
9.95
65.34
------------
65.59
5.19
---------
5.18
8.91
---------
9.00
9.81
---------
9.95
IIg
IIh
64.98
------------
65.13
4.94
---------
4.97
9.31
---------
9.21
9.95
------------
10.18
Table 2. IR and 31P{1H} NMR spectral data for bis(diphenylphosphorylated) diureas [Ph2P(O)NHC(O)NH]2Z IIa–IIh
IR, cm–1
ν C=O
1690
1675
31P{1H} NMR
Compound
ν P=O
1190
ν NH
3090, 3335
solvent
δ, ppm
IIa
IIb
IIc
IId
IIe
IIf
(CD3)2SO
15.01 s
15.27 s
14.44 s
15.89 s
15.22 s
15.42 s
33.40 s
1180
3070, 3140, 3320
3090, 3200, 3340
3080, 3140, 3220, 3250
3080, 3280
The same
1195, 1220
1175
1650, 1690
1700
"
"
1185
1710, 1690sh
1690
"
1195
3080, 3350
"
IIg
IIh
1180
1675
3070, 3320
CF3COOD
(CD3)2SO
1190
1690
3080, 3290, 3320
15.38 s
15.44 s
nylphosphine in 7 mL of freshly distilled CCl4. The for 1 h at ambient temperature, 60 mL of distilled water
was added, and the mixture was stirred for 1 h at ambi-
ent temperature and allowed to stand overnight. The
precipitate was filtered off; washed successively with a
mixture of 17 mL of distilled water and 3 mL of MeCN,
a mixture of 28 mL of 1% hydrochloric acid and 2 mL
of MeCN, and then distilled water (5 × 80 mL); and
dried in air.
mixture was stirred additionally for 20 min at the same
temperature, and the solvent and other volatile compo-
nents were removed in a vacuum. The residue was dis-
solved in 25 mL of dry MeCN, 0.040 g (0.42 mmol) of
finely ground anhydrous MgCl2 was added to the
resulting solution, and the mixture was stirred until
complete dissolution of the salt; 2.16 g (0.033 mol) of
NaOCN was added, and the mixture was stirred for 1 h
at ambient temperature. To the resulting suspension,
8.25 mmol of diamine (in the case of solid diamines,
their solutions in a minimal amount of anhydrous
ACKNOWLEDGMENTS
This work was supported by the Russian Foundation
MeCN were used) was added; the mixture was stirred for Basic Research (project no. 05–03–08017) and the
DOKLADY CHEMISTRY Vol. 419 Part 2 2008

90
GORYUNOV et al.
5. Safiulina, A.M., Goryunov, E.I., Baulina, T.V.,
Goryunova, I.B., Letyushev, A.A., Tananaev, I.G., and
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KhT'07 (Chemical Technology, Abstracts of Papers of
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2007, vol. 4, pp. 31–33.
Russian Academy of Sciences (Basic Research Pro-
gram no. 8 of the Presidium of the RAS, “Development
of Methods of Preparation of Chemical Compounds
and Design of New Materials”).
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