ISSN 1070-3632, Russian Journal of General Chemistry, 2011, Vol. 81, No. 4, pp. 777–778. © Pleiades Publishing, Ltd., 2011.
Original Russian Text © Yu.N. Mitrasov, O.V. Kondrat’eva, N.A. Lukicheva, I.V. Gordeeva, A.G. Kirillov, 2011, published in Zhurnal Obshchei Khimii,
2011, Vol. 81, No. 4, pp. 687–688.
LETTERS
TO THE EDITOR
Reactions of Amino Acids with Arylchlorophosphoranes
and Chlorophosphonium Compounds
Yu. N. Mitrasov, O. V. Kondrat’eva, N. A. Lukicheva, I. V. Gordeeva, and A. G. Kirillov
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/S1070363211040293
It is known that one of the general and accessible
synthesis methods for organylphosphonic acids
dichloride, which are the key compounds of organo-
phosphorus synthesis [1], is the reaction of chloro-
phosphonium compounds I (adducts of alkenes with
phosphorus pentachloride) and organylchlorophos-
phoranes II with various oxygen-containing com-
pounds [2]. In the development of this method the use
of the reagents with different nucleophilic centers as
the transformers of chlorides I and II into organyl-
dichlorophosphonates is promising. We have shown
that amino acids can be used as such compounds.
The reactions of organyltrichlorophosphonium hexa-
chlorophosphates Ia–If and chlorophosphoranes IIa–
IIg with amino acids were carried out at a molar ratio
of reagents 1:(2–1). The reaction proceeds rapidly at
20–25°C for 0.1–0.2 h. The amino acid chloride
hydrochlorides formed as yellow-orange solutions or
precipitates. The composition of compounds was
confirmed by the qualitative and quantitative analysis,
and also by the data of infrared spectra, which contain
the absorption bands of stretching and bending
vibrations of C=O (1716–1736 cm–1) and N–H bonds
(3150–3305, 1610–1658 cm–1).
NH3
_
RPCl2
+
RPCl3 PCl6
RCHCOO
O
Iа−If
IIIа−IIIf
_RCHCOCl,
_
ArnPCl5 n
_
ArnPCl3 n
NH3Cl
_POCl3
IIа−IIg
O
IVа−IVg
(f);
Iа–If, IIIа–IIIf: R = C6H5CH=CH (а), C6H5C(СН3)=CH (b), C2H5ОCH=CH (c), C4H9CHClCH2 (d), C5H11CHClCH2 (e),
O
IIa–IIg, IVа–IVg: n = 1, Ar = C6H5 (a), 4-CH3C6H4 (b), 4-FC6H4 (c), 4-ClC6H4 (d), C6H5CH=CH (e); n = 2, Ar = C6H5 (f), C6H5CH=CH (g).
After the precipitate separation, the filtrate was
distilled to yield organylphosphonic dichlorides IIIa–
IIIf, IVa–IVe and diarylphosphinic acids chlorides
IVf, IVg.
contains the characteristic absorption bands of
stretching vibrations of C=C, P=O, and P–Cl bonds at
1600, 1265, 565, 512 cm–1, respectively. Vibrations of
the aromatic ring appear as characteristic bands of the
C–H and C–C bonds. In the 31P NMR spectrum there
is a signal of phosphorus atom at δР 33 ppm.
The structure of compounds IIIa–IIIf and IVa–IVg
was confirmed by the IR and 31Р NMR spectroscopy,
and the composition, by the elemental analysis. Thus,
the IR spectrum of styryldichlorophosphonate IIIe
The IR spectra were recorded on an infrared
Fourier spectrometer FSM-1202 (KBr prisms, thin
777
Mitrasov
