ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 775–776. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Yu.N. Mitrasov, O.V. Kondrat’eva, N.A. Lukicheva, I.V. Gordeeva, 2011, published in Zhurnal Obshchei Khimii, 2011, Vol. 81,
No. 4, pp. 685–686.
LETTERS
TO THE EDITOR
Reactions of Chlorophosphonium Compounds
with Sodium N,N-Diethylamidodithiocarbamate
Yu. N. Mitrasov, O. V. Kondrat’eva, N. A. Lukicheva, and I. V. Gordeeva
Yakovlev Chuvash State Pedagogical University, ul. K. Marksa 38, Cheboksary, 428000 Russia
е-mail: mitrasov_un@mail.ru
Received December 23, 2010
DOI: 10.1134/S1070363211040281
The reactions of phosphorus pentachloride with
various C-, N-, O-, and S-nucleophiles are widely used
for the synthesis of compounds containing one or more
phosphorus-carbon bonds [1]. A feature of this method
is its proceeding in two stages: the first is the formation
of organyltrichlorophosphonium hexachlorophosphates
Ia–Ie, and the second is the formation of the stable
phosphorus chlorides III and IV at the treatment of the
hexachlorophosphates with appropriate reagents [2].
However, the universal transformers that meet the
modern production requirements were not developed
so far despite a wide range of those proposed. Analysis
of published data showed that the stage of
hexachlorophosphates Ia–Ie transformation into organyl-
dichlorothiophosphonates is the least known. The
known reagents (phosphorus pentasulfide, hydrogen
sulfide, ethylene sulfide, alkanethiols, and sodium
alkylxanthogenates) are of limited use due to the
different reasons: low accessibility, high toxicity, flam-
mability, multistage process, a large number of
unutilizable waste, the process duration, and in some
cases because of low yields. Therefore, in order to find
new, more efficient and technologically advanced
transformers, we studied the reaction of hexa-
chlorophosphates Ia–Ie with sodium N,N-diethyl-
amidodithiocarbamate.
precipitate separation, the filtrate was distilled to
isolate the organylphosphonic acids dichlorides IIa–IIe.
_
2NaSC(S)N(C2H5)2
+
RPCl2
RPCl3 PCl6
_2ClC(S)N(C2H5)2
_
PSCl
S
2NaCl,
3
Iа−Ie
IIа−IIe
R = C6H5CH=CH (а), C6H5C(СН3)=CH (b), C2H5ОCH=CH
(c), C4H9CHClCH2 (d), C5H11CHClCH2 (e).
The structure of the synthesized compounds was
confirmed by the IR and NMR spectroscopy, and the
composition, by the elemental analysis. The IR spectra
of dichlorides IIa–IIe contain the characteristic
absorption bands originating from the stretching
vibrations of P=S (680–685 cm–1) and P–Cl bonds
(475–525 cm–1) together with the absorption bands of
the hydrocarbon substituent (R). In the 31P NMR
spectra the phosphorus atom is characterized by the
chemical shift of 66–82 ppm, which is consistent with
the published data [3].
The IR spectra were recorded on an infrared
Fourier spectrometer FSM (KBr prisms, thin film).
1
The H NMR spectra were registered on a Bruker
WM-250 (250 MHz) instrument with internal refe-
rence dimethyl sulfoxide, the solvent (CD3)2SO, the
31P NMR spectra, on a Bruker WP-80 (32.44 MHz) in-
strument with external reference 85% phosphoric acid.
The interaction of organyltrichlorophosphonium
compounds Ia–Ie with sodium N,N- diethylamido-
dithiocarbamate was performed at a molar ratio of
reagents 1:2. The reaction proceeds rapidly at 20–25°C
for 0.1–0.2 h after the reagents mixing. The yellow-
orange solutions and sodium chloride precipitate are
formed, which is confirmed by a qualitative detection
of sodium and chloride ions, as well as by the
quantitative determination of chlorine. After the
ACKNOWLEDGMENTS
This work was supported by the Analytical
Departmental Target Program “Development of
Scientific Potential of Higher School (2009–2011
years)” (project no. 2.1.1/1979).
775
Mitrasov
