440 Prishchenko et al.
in diethyl ether, 30 mL, was added to a solution
of phosphorus trichloride, 6.5 g in diethyl ether,
15 mL under stirring and cooling at −20◦C. Hexane,
30 mL was added to a mixture, the white crystals of
bis(chloromethyl)amine were isolated and washed
with hexane, 30 mL. Then methylene chloride, 30 mL
was added to the crystals of amine; the mixture was
cooled to −30◦C; and a solution of O,O-diisopropyl
methyl phosphonite, 8.3 g in 20 mL of methylene
chloride was added under stirring. The mixture was
heated and refluxed for 0.5 h; the solvent was re-
moved and the residue was distilled in a vacuum to
give 5.5 g of bisphosphinate 49.
chloride and hexane. The white crystals were kept
in a vacuum (1 mmHg) for 0.5 h to obtain 5 g of
bisphosphonate 54.
REFERENCES
[1] Moedritzer, K.; Irani, R. R. J Org Chem 1966, 31,
1603–1607.
[2] Petrov, K. A.; Chauzov, V. A.; Erokhina, T. S. Usp
Khim 1974, 43, 2045–2085 (in Russian).
[3] Uziel, J.; Jenet, J. P. Zh Org Khim 1997, 33, 1605–
1627 (in Russian).
[4] Kukhar, V. P.; Hudson, H. R. Aminophosphonic and
Aminophosphinic Acids. Chemistry and Biological
Activity; John Wiley and Sons: New York, 2000.
[5] Kolodiazhnyi, O. I. Usp Khim 2006, 75, 254–282 (in
Russian).
[6] Fields, S. C. Tetrahedron 1999, 55, 12237–12273.
[7] Hilgetag, G.; Martini, A. Weygand- Hilgetag.
Organisch-Chemische Experimentierkunst; Khimia:
Moscow, 1968 (in Russian).
/
N,N -Bis(methoxymethyl)piperazine (50). A mix-
ture of piperazine, 8.6 g; paraformaldehyde, 6 g;
and methanol, 100 mL was refluxed for 2 h. Then
potassium carbonate, 7 g was added under stirring,
and the mixture was left for 12 h. The organic layer
was separated, the solvent was evaporated, and the
residue was crystallized from a mixture of diethyl
ether and hexane to give 13.6 g of piperazine 50.
[8] Kabachnik, M. I.; Medved, T. Ya. Dokl Akad Nauk
1952, 83, 689 (in Russian).
[9] Fields, E. K. J Am Chem Soc 1952, 74, 1528.
[10] Petrov, K. A.; Maklyaev, F. L.; Bliznyuk, N. K. Zh
Obsh Khim 1959, 29, 591–594.
/
N,N -Bis(diethoxyphosphorylmethyl)piperazine
(51). A mixture of compound 50, 3.4 g; diethyl
phosphite, 6 g was heated at 100–110◦C until the
distillation of methanol was completed. The residue
was crystallized from a mixture of diethyl ether and
hexane. The white crystals were stored in a vacuum
(1 mmHg) for 0.5 h to obtain 6.9 g of compound
51.
[11] Belsky, F. I.; Goryunova, I. V.; Petrovsky, P. V.;
Medved, T. Ya.; Kabachnik, M. I. Izv AN SSSR Khim
1982, 103–109 (in Russian).
[12] Prishchenko, A. A.; Livantsov, M. V.; Novikova, O. P.;
Livantsova, L. I.; Petrosyan, V. S. Heteroat Chem
2010, 21, 71–77.
[13] Robinson, G. M.; Robinson, R. J Chem Soc 1923, 123,
532–543.
[14] Quintard, J.-P. Synthesis 1984, 495–498.
[15] Polikarpov, Yu. M.; Shcherbakov, B. K.; Medved,
T. Ya.; Kabachnik, M. I. Izv AN SSSR Khim 1978,
2114–2117 (in Russian).
[16] Matveev, S. V.; Matveeva, A. G.; Matrosov, E. I.;
Shcherbakov, B. K.; Polikarpov, Yu. M.; Kabachnik,
M. I. Izv RAN Khim 1994, 2007–2012 (in Russian).
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2465–2524.
[18] Troev, K. D. Chemistry and Application of H-
Phosphonates; Elsevier: Amsterdam, 2006.
Piperazines 52,53 were prepared similarly.
/
N,N -Bis[bis(trimethylsiloxy)phosphorylmethyl]-
piperazine (54). Trimethylsilyl chloride, 1 mL was
added to a mixture of compound 50, 1.7 g, and
tris(trimethylsilyl) phosphite, 9 g under stirring.
After the completion of the exothermic reaction
the mixture was heated at 70–90◦C for 1 h with
distillation of low-boiling compounds. The residue
was crystallized from a mixture of methylene
Heteroatom Chemistry DOI 10.1002/hc