Reaction of Bis(chloromethyl)phosphinoyl Chloride and Phenyl (Chloromethyl)phosphonochloridate with Diethyl Bis(trimethylsilyl) phosphoramidite [1]

Full text of DOI:10.1023/A:1023407409531

Russian Journal of General Chemistry, Vol. 73, No. 1, 2003, pp. 151 152. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 1, 2003,
pp. 159 160.
Original Russian Text Copyright
2003 by M. Pudovik, Kibardina, A. Pudovik.
LETTERS
TO THE EDITOR
Reaction of Bis(chloromethyl)phosphinoyl Chloride
and Phenyl (Chloromethyl)phosphonochloridate
with Diethyl Bis(trimethylsilyl)phosphoramidite
M. A. Pudovik, L. K. Kibardina, and A. N. Pudovik
Arbuzov Institute of Organic and Phisycal Chemistry, Kazan Research Center,
Russian Academy of Sciences, Kazan, Tatarstan, Russia
Received April 5, 2002
It was found that the reactions of bis(chloromethyl)-
phosphinoyl chloride (Ia) or phenyl (chloromethyl)-
phosphonochloridate (Ib) with diethyl bis(trimethyl-
silyl)phoshoramidite (II) are accompanied by libera-
tion of chlorotrimethylsilane and formation of tri-
methylsilyl bis(chloromethyl)phosphinate (VIa) or
trimethylsilyl phenyl (chloromethyl)phosphonate
(VIb), respectively.
Phosphorimidate IV reacts with the starting com-
pounds Ia and Ib to form intermediates Va and Vb,
which, as previously shown [1], undergo -cleavage
to give final products VIa and VIa, as well as oligo-
meric product VII.
a
IIIa + O=P(NEt2)3
VIII
Ia + P(NEt2)3
O
O
b
(Et2N)2PCl + (ClCH2)2PNEt2
R(ClCH2)PCl + (EtO)2PN(SiMe3)2
IX
X
Ia, Ib
II
OSiMe3
The oxidative ability of phosphinoyl chloride Ia
toward P(III) derivatives was also illustrated by study-
ing its reaction with hexaethylphosphorous triamide
by 31P NMR spectroscopy. In this case, both redox
R(ClCH2)PCl + (EtO)2P=NSiMe3
IIIa, IIIb
IV
O
[IIIa ( 98 ppm) and VIII ( 24 ppm)] and ex-
P
change reaction products [IX ( P 160 ppm) and X
N^
P
RP
P(OEt)2
Ia + IV
(
36 ppm)] were detected.
Me3SiCl
P
ClCH2 OSiMe3
Trimethylsilyl bis(chloromethyl)phosphinate
O
(VIa). A mixture of 3.63 g of compound Ia and
5.62 g of compound II was heated for 3 h at 140 C.
Fractionation in a vacuum gave 1.3 g (55%) of com-
R(ClCH2)POSiMe3 + [(EtO)2P N]n
VIa, VIb
pound VIa, bp 68 C (0.06 mm), n2D0 1.4530 [1]. 31P
R=ClCH2 (a), PhO (b).
NMR spectrum: P 26 ppm. 1H NMR spectrum (CCl4),
3
, ppm: 0.49 s (9H, CH3Si), 3.83 d (4H, CH2P, JHCP
The 31P NMR spectrum of the reaction mixture of
phosphinoyl chloride Ia and phosphoroamidite II
contains signals of trimethylsilyl phosphinate VIa (
26 ppm), bis(chloromethyl)phosphinous chloride
6 Hz). Found, %: P 13.26. C5H13Cl2O2PSi. Calculated,
%: P 13.18.
P
Phenyl trimethylsilyl (chloromethyl)phospho-
nate (VIb) was obtained analogously from 4.5 g of
compound Ib and 5.62 g of compound II. Yield
(IIIa) ( 98 ppm), and residual phosphoramidite II.
P
The experimental evidence obtained suggests that the
first stage of the reaction involves oxidation of phos-
phoroamidite II to diethyl trimethylsilyl (trimethyl-
silyl)phosphorimidate (IV) and, corresponingly,
reduction of compound Ia and Ib to compounds
IIIa and IIIb, respectively.
2.25 g (81%), bp 75 C (0.02 mm), n2D0 1.5217 [1]. 31P
1
NMR spectrum:
5 ppm. H NMR spectrum (CCl4),
P
3
, ppm: 0.47 s (9H, CH3Si); 3.83 d (2H, CH2P, JHCP
6 Hz), 7.23 m (5H, CHarom). Found,%: P 11.22.
C10H16ClO3PSi. Calculated,%: P 11.13.
1070-3632/03/7301-0151$25.00 2003 MAIK Nauka/Interperiodica

152
PUDOVIK et al.
1
The H NMR spectra were recorded on a Varian
T-60 spectrometer (60 MHz) against internal TMS.
The 31P NMR spectra were measured on a KGU-4
spectrometer (10.2 MHz) against external 85% phos-
phoric acid.
Foundation for Basic Research (project no. 00-03-
32837).
REFERENCES
1. Pudovik, M.A., Kibardina, L.K., and Pudovik, A.N.,
Zh. Obshch. Khim., 1996, vol. 66, no. 11, pp. 1017
1918.
ACKNOWLEDGMENTS
The work was financially supported by the Russian
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 1 2003