A new versatile synthesis of functionalized phosphine oxides-efficient ligands for rare-earth metals extraction

Article abstract of DOI:10.1080/10426507.2010.515955

A new approach to the synthesis of 2-hydroxyaryl-alkenylphosphine oxides and dialkyl (diaryl)-(2-methyl-4-oxopent-2-yl)phosphine oxides was developed that involves an interaction of Grignard reagents with available benzo[e]-1,2-oxaphosphorinines and 1,2- oxaphospholene-2-oxide. This approach allows obtaining target compounds with a high yield. The synthesized phosphine oxides proved to be highly efficient extractants in the micellar extraction of some lanthanides from the nitric acid media. Copyright Taylor & Francis Group, LLC.

Full text of DOI:10.1080/10426507.2010.515955

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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A New Versatile Synthesis
of Functionalized Phosphine
Oxides—Efficient Ligands for Rare-Earth
Metals Extraction
D. A. Tatarinov a b , V. F. Mironov a b , A. A. Kostin a b , A. V.
Nemtarev a b , T. A. Baronova a , B. I. Buzykin a & Yu. G. Elistratova a
a A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan
Scientific Centre , Russian Academy of Sciences , Kazan , Russian
Federation
b Kazan (Volga region) Federal University , Kazan , Russian
Federation
Published online: 25 Apr 2011.
To cite this article: D. A. Tatarinov , V. F. Mironov , A. A. Kostin , A. V. Nemtarev , T. A. Baronova ,
B. I. Buzykin & Yu. G. Elistratova (2011) A New Versatile Synthesis of Functionalized Phosphine
Oxides—Efficient Ligands for Rare-Earth Metals Extraction, Phosphorus, Sulfur, and Silicon and the
Related Elements, 186:4, 694-697, DOI: 10.1080/10426507.2010.515955
To link to this article: http://dx.doi.org/10.1080/10426507.2010.515955
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Phosphorus, Sulfur, and Silicon, 186:694–697, 2011
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2010.515955
A NEW VERSATILE SYNTHESIS OF FUNCTIONALIZED
PHOSPHINE OXIDES—EFFICIENT LIGANDS FOR
RARE-EARTH METALS EXTRACTION
D. A. Tatarinov,1,2 V. F. Mironov,1,2 A. A. Kostin,1,2
A. V. Nemtarev,1,2 T. A. Baronova,1 B. I. Buzykin,1
and Yu. G. Elistratova1
1A. E. Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific
Centre, Russian Academy of Sciences, Kazan, Russian Federation
2Kazan (Volga region) Federal University, Kazan, Russian Federation
Abstract A new approach to the synthesis of 2-hydroxyaryl-alkenylphosphine oxides and
dialkyl (diaryl)-(2-methyl-4-oxopent-2-yl)phosphine oxides was developed that involves an
interaction of Grignard reagents with available benzo[e]-1,2-oxaphosphorinines and 1,2-
oxaphospholene-2-oxide. This approach allows obtaining target compounds with a high yield.
The synthesized phosphine oxides proved to be highly efficient extractants in the micellar
extraction of some lanthanides from the nitric acid media.
Keywords Lanthanide; micellar extraction; organomagnesium reagents; oxaphospholene;
oxaphosphorinine; phosphine oxide
A trend of modern chemistry is the development of a highly efficient and selective pathway
of synthesis of the target compounds with the high potential of practice application. Phos-
phine oxides are widely used as the ligands for the metal complex catalysts,1–3 extracting
agents for rare-earth metals,4–6 and for a creation of the ion-selective electrodes.7,8 It is
known that the basicity and the complexing properties of the phosphine oxide phosphoryl
group are strongly influenced by the electronic effect of substituents at the phosphorus
atom. The complexing properties of ligands depend on the presence of the various func-
tional groups in the molecule. Thus, the diversity range of the substituents and functional
group can increase the complexing properties of the phosphine oxide ligands and improve
their selectivity.
In this work we realized a new synthetic approach to the functionally substituted phos-
phine oxides, which is based on the reactions of such available phosphorus heterocycles, as
4-aryl-2,6-dichlorobenzo[e]-[1,2]oxaphosphinine-2-oxides 1 and 2-chloro-3,3,5-trimethyl-
1,2-oxaphospholene-2-oxide 2 with the organomagnesium compounds.
Received 8 July 2010; accepted 9 August 2010.
The work was supported by the Russian Foundation for Basic Research and Tatarstan Academy of Sciences
(grant No. 09-03-97007-r a) and by a grant from the president of the Russian Federation (MK-1172.2010.3).
Address correspondence to D. A. Tatarinov, A. E. Arbuzov Institute of Organic and Physical Chemistry,
Kazan Scientific Centre, Russian Academy of Sciences, Arbuzov str. 8, 420088 Kazan, Russian Federation.
E-mail: datint@iopc.ru
694

RARE-EARTH METALS EXTRACTION
695
Six-membered heterocycles 1, bearing one endocyclic phosphorus-carbon bond, are
easily available from the reaction of 2,2,2-trichlorobenzo[d]-1,3,2-dioxaphosphole 3 with
the arylacetylenes.9 The Michaelis chloride 2 is another easily accessible heterocycle con-
taining one endocyclic phosphorus-carbon bond.10,11
O
OH
O
1) 2R1MgX
2) H2O, H+
O
P
R1
R1
P
Cl
Cl
Cl
R
4
R
1a,b
R = Ph; a) R1 = Ph, b) Et, c) Pr; R = 1-naphthyl; d) R1 = Ph, e) CH2Ph
Scheme 1
Earlier we found that the interaction of the compounds 1 with Grignard reagents leads
to the formation of phosphine oxides 4a–e.12,13 The reaction gives rise to the substitution of
both exocyclic P–Cl and endocyclic P–O bonds and allows us to obtain the phosphine oxides
with the hydroxy-group in δ-position to the phosphorus atom (Scheme 1). Z-Configuration
of double bond of the alkenyl fragment is predetermined by the initial phosphorinine
structure.
We extended the utilization of the approach to the diversity range of the known
and new oxaphosphorinines and Grignard reagents. So, 1,2-oxaphosphinines 1c–e9 were
synthesized with this purpose for the first time. They were prepared by the reaction of
dioxaphosphole 3 with various arylacetylenes (Scheme 2).
O
O
O
O
P
ArC CH
PCl3
Cl
Cl
Ar
1c-e
3
Ar = 4-cyclo-C6H11-C6H4 (c), 3-Br-C6H4 (d), 2-Me-C6H4 (e)
Scheme 2
It is interesting to note that in 31P NMR spectra of compounds 1b and 1e we observed
two signals with equal intensity. A similar picture was also observed in the proton and
carbon spectra. Analysis of NMR data allows the conclusion that the doubling is caused
by a diastereoisomerism of these compounds (Scheme 3), which connected with the chi-
ral phosphorus atom and atropisomerism along C–C bond. The last phenomenon is not
observed for compounds 1c and 1d.
It was found that altering the nature of the substituents at the different positions of
the phosphorinine’s molecule and using various organomagnesium reagents, prepared from
simple aryl or non-branched alkyl halides, does not influence the course of the reaction
(Scheme 4). In all cases the target phosphine oxides 4 were obtained with a high yield
(85–95%).
Due to their structural peculiarities, the phosphine oxides 4, bearing phosphoryl
and hydroxyl groups at the one side of the double bond can, be effective ligands for
the extraction of ions of various metals. This proposition was confirmed by the effective

696
D. A. TATARINOV ET AL.
O
O
O
O
P
P
Cl
Cl
Cl
Cl
Me
Me
1e
Scheme 3
O
X
OH
O
X
1) 2R1MgX
2) H2O, H+
O
P
P
R1
R1
Cl
Cl
Cl
R
4
R
1
R1 = Aryl, Alkyl; R = Aryl; X = H, Me
Scheme 4
micellar extraction of the range lanthanides ions by the some of the obtained phosphine
oxides. They exhibit a high extraction degree in the nitric acid media (pH ∼ 1), which
reaches about 100% in some cases.14
We also extend our approach to other phosphorus heterocycles. Recently it was found
that the reaction of 2-chloro-3,3,5-trimethyl-1,2-oxaphospholene-2-oxide 2 with benzyl-
and hexylmagnesium halides gives rise to the formation of dialkyl(2-methyl-4-oxopent-
2-yl)-phosphine oxides.15 The reactions of the various alkyl- and arylmagnesium halides
turned out to give dialkyl(diaryl)-(2-methyl-4-oxopent-2-yl)-phosphine oxides 5 with a
high yield (>90%) in all cases (Scheme 5). The formation of 3-oxoalkylphosphine oxides
6 occurs through the intermediate magnesium salt 5, which further was converted into the
6 as the result of hydrolysis.
O
O
MgX
O
O
O
P
H2O, H+
–MgClX
R
R
2RMgX
R
O
P
P
Cl
R
6
2
5
R = alkyl, aryl
Scheme 5
CONCLUSIONS
A new synthetic approach to the functionalized phosphine oxides that is based on
the reactions of available phosphorus heterocycles bearing one endocyclic P–C bond was
developed. The extracting properties of the obtained phosphine oxides were tested and
showed a high efficiency for the micellar extraction from the acid media.

RARE-EARTH METALS EXTRACTION
697
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