One-pot atom-economic synthesis of thioselenophosphinates via a new multicomponent reaction of secondary phosphanes with elemental sulfur, selenium, and amines

Article abstract of DOI:10.1002/ejoc.201001189

The multicomponent reaction between secondary phosphanes R₂PH (R = Ph, arylalkyl, hetarylalkyl), elemental sulfur, selenium, and primary, secondary, or tertiary amines to afford the corresponding mono-, di-, and trialkylammonium thioselenophosphinates has been discovered. The atom-economic reaction proceeds under mild conditions (ethanol/toluene, 40-70 °C, 40 min) to give the target alkylammonium thioselenophosphinates in high yields (up to 94%). A family of hitherto unknown mono-, di-, and trialkylammonium thioselenophosphinates has been synthesized in high yields under mild conditions through a novelmulticomponent atom-economic reaction between secondary phosphanes, elemental sulfur, selenium, and primary, secondary, or tertiary amines.

Full text of DOI:10.1002/ejoc.201001189

SHORT COMMUNICATION
DOI: 10.1002/ejoc.201001189
One-Pot Atom-Economic Synthesis of Thioselenophosphinates via a New
Multicomponent Reaction of Secondary Phosphanes with Elemental Sulfur,
Selenium, and Amines
Alexander V. Artem’ev,[a] Nina K. Gusarova,[a] Svetlana F. Malysheva,[a]
Victor I. Mamatyuk,[b] Yurii V. Gatilov,[b] Igor A. Ushakov,[a] and Boris A. Trofimov*[a]
Keywords: Phosphanes / Sulfur / Selenium / Amines / Multicomponent reactions
The multicomponent reaction between secondary phos-
phanes R2PH (R = Ph, arylalkyl, hetarylalkyl), elemental sul-
fur, selenium, and primary, secondary, or tertiary amines to
afford the corresponding mono-, di-, and trialkylammonium
thioselenophosphinates has been discovered. The atom-
economic reaction proceeds under mild conditions (ethanol/
toluene, 40–70 °C, 40 min) to give the target alkylammonium
thioselenophosphinates in high yields (up to 94%).
Introduction
The chemical and coordinating properties of anionic li-
gands R2PCh2– with phosphorus and sulfur or selenium do-
nor atoms (Ch = S, Se) are well documented.[1] Dithiophos-
–
–
phinates R2PS2 and diselenophosphinates R2PSe2 , where
R = alkyl or aryl, are known and widely used as single-
source precursors of remarkable nanomaterials,[4,5] ligands
for metal complexes,[6,7] lubricant oil additives,[2] extraction
agents for the separation of heavy metals,[3] as well as key
starting materials for the synthesis of practically important
organophosphorus and organochalcogen compounds.[1b,8]
At the same time, mixed thioselenophosphinate salts
R2PSeS– with sulfur and selenium are virtually neglected
due to their unavailability.[9–12] For example, the most mod-
ern synthesis for ammonium thioselenophosphinates[13] in-
volves utilizing moisture- and air-sensitive phenyldichlor-
phosphane, Grignard and organolithium reagents, and in-
accessible 2-(trimethylsilyl)ethanethiol. A limitation of the
above procedure is that it allows only tetraalkylammonium
salts to be synthesized (Scheme 1).
Scheme 1. Multistep synthesis of tetraalkylammonium thioseleno-
phosphinates.
thioselenophosphanoic acids on the basis of a novel multi-
component atom-economic reaction of secondary phos-
phanes with elemental sulfur, selenium, and amines.
Results and Discussion
Therefore, the development of a direct, mild, and orga-
nometallic-free method for the preparation of ammonium
thioselenophosphinates is highly desirable. In this paper, we
report an original shortcut to alkylammonium salt of
We have found that secondary phosphanes 1–7 readily
react with elemental sulfur, selenium, and amines under
mild conditions (40–70 °C, 40 min, inert atmosphere) in
ethanol/toluene to afford various alkylammonium salts of
thioselenophosphanoic acids 8a–l in high yields (76–94%,
Table 1).
As seen from Table 1, secondary phosphanes with vari-
ous substituents as well as primary, secondary, and tertiary
amines participate readily in this multicomponent reaction.
The generality and preparative efficiency of the method de-
veloped have been demonstrated by the synthesis of an ear-
lier unknown series of mono-, di-, and trialkylammonium
salts of thioselenophosphanoic acids.
[a] A. E. Favorsky Irkutsk Institute of Chemistry,
Siberian Branch of the Russian Academy of Sciences,
1 Favorsky Str., 664033 Irkutsk, Russian Federation
Fax: +7-3952-419346
E-mail: boris_trofimov@irioch.irk.ru
[b] N. N. Vorozhtsov Novosibirsk Institute of Organic Chemistry,
Siberian Branch of the Russian Academy of Sciences,
630090 Novosibirsk, Russian Federation
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201001189.
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B. A. Trofimov et al.
SHORT COMMUNICATION
Table 1. One-pot synthesis of thioselenophosphinates from second- ethylammonium and adopts a monomeric structure in the
ary phosphanes, elemental sulfur, selenium, and amines.[a]
solid state (Figure 1). The phosphorus atom adopts a
slightly distorted tetrahedral structure with the bond angles
ranging between 99.8 and 120.0°. The sulfur and selenium
atoms are disordered and refined with 50% occupancy for
both atoms as observed for the similar structures.[5f,13] The
phosphorus–selenium bond length (2.10 Å) within the
thioselenophosphinite unit are intermediate between single
(P–Se 2.26 Å)[16] and double (P=Se 2.09 Å)[17] bonds, which
is indicative of delocalization of the negative charge across
the [PSeS]– moiety. The phosphorus–sulfur distance
(2.02 Å) lies between the expected P–S single (2.09 Å) and
double (1.95 Å) bond lengths, which also confirms the delo-
calization over the triade [PSeS]–. This delocalization is ob-
served in solution by using 31P and 77Se NMR spec-
troscopy. In the 31P NMR spectrum, a singlet (at 43–
49 ppm) with one typical satellite pair is present (1JP,Se
=
560–606 Hz). In the 77Se NMR spectrum, the signals
1
(doublet, JP,Se = 560–606 Hz) of the selenium atom in the
P–Se bond of thioselenophosphinates were observed in the
1
range of –83 to 4 ppm. The JP,Se value (560–606 Hz) is in-
termediate between the coupling constant values for single
(200 to 600 Hz) and double (800 to 1200 Hz) P–Se
bonds,[18] thus corresponding to the 1.5 order of the phos-
phorus–selenium bonds. The IR spectra show the absorp-
tion bands in the region of 500–600 cm–1, assignable to P–
S bond, as well as the bands in the region of 400–500 cm–1,
which are typical for P–Se bonds. Elemental analysis of all
the compounds isolated corresponds to their structures.
[a] All experiments were carried out at 40–70 °C in ethanol/toluene
under an argon blanket; the ratio of secondary phosphane/S/Se/
amine was 1.1:1:1:1.1. [b] All yields refer to isolated products.
[c] Secondary phosphane 2 was used as a mixture of diastereomers.
The advantages of this method are the following: simple
experimental procedure, short reaction time (40 min), and
mild reaction conditions (40–70 °C, ethanol/toluene). In ad-
dition, the reaction found avoids the use of toxic phospho-
rus halides and flammable and hazardous organometallic
reagents and inaccessible synthons such as 2-(trimethyl-
silyl)ethanethiol. Taking into account that starting second-
ary phosphanes 1–7 are readily available from red phospho-
rus and vinylarenes or vinylhetarenes (styrenes,[14] vinyl-
pyridines,[15] or vinylfuranes[14a]), the multicomponent as-
sembly here presented may be considered as one of the most
concise and expedient approaches to thioselenophosphin-
ates so far know.
Figure 1. Thermal ellipsoid plot (50% probability) of the structure
of 8h (S1A, S2A, Se1, Se2 atoms are shown as balls because of
disorder).
The synthesized alkylammonium thioselenophosphinates
8a–l are white powders, stable at room temperature, soluble
in most of organic solvents, and insoluble in diethyl ether
and in water (accept for thioselenophosphinate 8i). Their
structure unambiguously follows from the X-ray analysis
1
data and 31P, 77Se, H, and 13C NMR spectra.
The tentative mechanism of the multicomponent reac-
X-ray crystallographic studies of thioselenophosphinate tion found can be rationalized as follows (Scheme 2). In
8h have shown that it crystallizes as an ionic salt in the stage 1, secondary phosphane 1–7 reacts with elemental se-
monoclinic P21/n space group. Selected bond lengths and lenium to give secondary phosphane selenide A. The latter
angles are presented in the Experimental Section. The mole- is deprotonated by the amine to afford selenophosphinite B
cule of this salt is formed by the anion of bis(2-phen- (stage 2), which further reacts with elemental sulfur to pro-
ethyl)thioselenophosphanoic acid and the cation of tri- vide thioselenophosphinate 8 (stage 3).
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One-Pot Atom-Economic Synthesis of Thioselenophosphinates
Supporting Information (see footnote on the first page of this arti-
cle): General Remarks and characterization data for compounds
8a–l.
Acknowledgments
This work has been carried out under the financial support of the
President of the Russian Federation under the leading scientific
schools (Grant NSh-3230.2010.3) and young Russian scientists
(grant MK-629–2010.3) programs.
Scheme 2. Probable mechanism of alkylammonium thioseleno-
phosphinates formation.
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Conclusions
[2] L. R. Rudnic, Lubricant Additives: Chemistry and Applications,
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In summary, the efficient one-pot synthesis of alkylam-
monium thioselenophosphinates has been developed and
proceeds through a novel multicomponent atom-economic
reaction between secondary phosphanes, elemental sulfur,
selenium, and amines. The salts synthesized are promising
intermediates to produce single-source precursors of metal
chalcogenide nanoparticles, ligands for design of metal
complexes and supramolecular structures, prospective ex-
tractants of heavy elements, potentially biological active
compounds, convenient model compounds for the investi-
gation of SPSe-triade ambident reactivity, as well as the key
starting materials for the preparation S-alkyl esters and Se-
alkyl esters of thioselenophosphanoic acids.
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Experimental Section
General Procedure for the Preparation of Thioselenophosphinates
8a–l: To a solution of secondary phosphane 1–7 (1.1 mmol) in
EtOH (7 mL) was added amorphous grey selenium (78.9 mg,
1.00 mmol), and the mixture was stirred for 20 min at 40 °C until
dissolution of the residue. To the transparent solution obtained, a
solution of elemental sulfur (32.1 mg, 1.00 mmol) in toluene (3 mL)
and a solution of amine (1.1 mmol) in EtOH (2 mL) were consecu-
tively added. The resultant solution was stirred for 20 min at 70 °C.
The solvents were removed under reduced pressure, and the residue
was washed with Et2O (2ϫ10 mL). The latter was decanted, and
the white powder was dried in vacuo (1 Torr, 40–45 °C) to afford
corresponding salt 8a–l.
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Crystal Data for 8h: C18H30NO2PSSe, M = 434.42, monoclinic,
space group P21/n, a = 10.8883(3) Å, b = 10.4399(3) Å, c =
18.6420(6) Å, β = 91.091(1)°, V = 2118.70(11) Å3, Z = 4, Dcalcd.
= 1.362 gcm–3, µ = 1.956 mm–1, (2θ)max = 65.3°, data/restraints/
parameters: 7692/0/235, R indices [I = 2σ(I)]: R1 = 0.0530, wR2 (all
data) = 0.1629. Selected bond lengths [Å]: P1–C1 1.833(3), P1–C8
1.826(3), P1–S1A 2.048(5), P1–S2A 1.994(5), P1–Se1 2.1139(15),
P1–Se2 2.0823(10). Selected bond angles [°]: S2A–P1–S1A 114.6(2),
S1A–P1–Se2 115.76(15), S2A–P1–Se1 115.09(18), Se2–P1–Se1
117.64(5), C8–P1–C1 105.29(13).
CCDC-789465 contains the supplementary crystallographic data
for this paper. These data can be obtained free of charge from The
Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
Eur. J. Org. Chem. 2010, 6157–6160
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B. A. Trofimov et al.
SHORT COMMUNICATION
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Received: August 24, 2010
Published Online: October 11, 2010
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Eur. J. Org. Chem. 2010, 6157–6160