Synthesis of Phosphorus-Substituted Dialkylamides of Organophosphorus Acids, Containing P–C–N–P Moiety 499
(C3); 31P NMR spectrum, δ, ppm: 18.20 s (cf. [13]).
Repeated distillation of the low-boiling fraction gave
6.7 g of O,O-diethyl (diethoxymethyl)phosphonate
(11), yield 72%, bp 79◦C (1 mmHg), n2D01.4255. PCH
fragment: 1H NMR spectrum, δ, ppm: δ 4.55 d
(2 JPH = 5.0 Hz); 13C NMR spectrum, δC, ppm: 98.19
d (1 JPC = 207.0 Hz); δP 11.15 ppm (cf. [14]).
was added. The resulting mixture was left to stand
for 48 h at 20◦C. The solvent was removed, and the
residue was distilled in a vacuum to give 9.4 g of
phosphonate 14.
REFERENCES
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O,O-Diethyl N-(diethoxyphosphinothioyl)-N-
[2] Dunina, V. V.; Beletskaya, I. P. Zh Org Khim 1993,
29, 806–878 (in Russian).
[3] Melnikov, N. N.; Novozhilov, K. B.; Belan, S. R.
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[5] Prishchenko, A. A.; Livantsov, M. V.; Kustrya, D. N.;
Novikova, O. P.; Grigoriev, E. V.; Goncharova, Zh.
Yu. Zh Obsh Khim 1997, 67, 1914–1916 (in Russian).
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[7] Petrov, K. A.; Chauzov, V. A.; Agafonov, S. V. Usp
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[8] Lutsenko, I. F.; Prishchenko, A. A.; Livantsov, M. V.
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1998, 68, 1217–1218 (in Russian).
ethylaminomethylphosphonate (12a)
A mixture of 3.2 g of phosphonate 2b, 0.4 g of sulfur,
and 10 mL of benzene was heated on a water bath
for 1 h and then cooled. The residual sulfur was then
filtered off, the solvent was removed, and the residue
was distilled to give 2.9 g of phosphonate 12a.
Compounds 12b and 12c were obtained analo-
gously.
O,O-Diethyl N-[ethoxy(methyl)phosphinoyl]-N-
ethylaminomethylphosphonate (13)
To a solution of 4.2 g of phosphonate 2b in 15 mL of
ether, a solution of 6 g of methyl iodide in 5 mL of
ether was added dropwise with stirring at 10◦C. The
resulting mixture was refluxed for 1 h, the solvent
was removed, and the residue was distilled to give
3 g of phosphonate 13.
O,O-Diethyl N-methyl-N-(diethoxyphosphoryl)-
amino(phenyl)methylphosphonate (14)
To a solution of 4.5 g of benzal(methyl)amine in 15
mL of methylene chloride, a solution of 6.4 g of di-
ethyl chlorophosphate in 10 mL of methylene chlo-
ride was added dropwise with stirring at 10◦C. Af-
ter 30 min, diethyl trimethylsilyl phosphite, 8.6 g,
[14] Prishchenko, A. A.; Livantsov, M. V.; Moshnikov,
S. A.; Lutsenko, I. F. Zh Obsh Khim 1987, 57, 1910–
1912 (in Russian).
Heteroatom Chemistry DOI 10.1002/hc