Mendeleev Commun., 2016, 26, 397–398
2 (a) A. K. Bhattacharya and G. Thyagarajan, Chem. Rev., 1981, 81, 415;
O
(b) V. D. Romanenko, M. V. Shevchuk and V. P. Kukhar, Curr. Org.
Chem., 2011, 15, 2774.
PPh2
Me
Me
Ph2P(O)H
3 (a) K. Issleib and B. Walther, Angew. Chem., Int. Ed. Engl., 1967, 6, 88;
(b) V. I. Evreinov, V. E. Baulin, Z. N. Vostroknutova and E. N. Tsvetkov,
Russ. Chem. Bull., 1993, 42, 472 (Izv. Akad. Nauk, Ser. Khim., 1993,
518); (c) Yu. A. Veits, N. B. Karlstedt, A. V. Chuchuryukin and I. P.
Beletskaya, Russ. J. Org. Chem., 2000, 36, 570 (Zh. Org. Khim., 2000,
36, 778); (d) V. V. Ragulin, Russ. J. Gen. Chem., 2012, 82, 1928 (Zh.
Obshch. Khim., 2012, 82, 1973).
OSiMe3
4
3
3
Me3SiO
O
3
PPh2
PPh2
O
Me
Me
Me
Me
Ph2P–O–SiMe3 + Me2C=O
– HX
1
OH
4 (a) K. Issleib and B. Walther, J. Organomet. Chem., 1970, 22, 375;
(b) N. D. Gomelya and N. G. Feshchenko, J. Gen. Chem. USSR (Engl.
Transl.), 1991, 61, 2338 (Zh. Obshch. Khim., 1991, 61, 2521); (c) N. A.
Bondarenko and E. N. Tsvetkov, J. Gen. Chem. USSR (Engl. Transl.),
1989, 59, 1361 (Zh. Obshch. Khim., 1989, 59, 1533); (d) H. J. Brass,
R. A. DiPrete, J. O. Edwards, R. G. Lawier, R. Curci and G. Modena,
Tetrahedron, 1970, 26, 4555; (e) M. Sekine, M. Nakajima, A. Kume,
A. Hashizume and T. Hata, Bull. Chem. Soc. Jpn., 1982, 55, 224.
5 (a) X. Creary, C. C. Geiger and K. Hilton, J. Am. Chem. Soc., 1983, 105,
2851; (b) M. Hayashi, Y. Matsuura, Y. Nishimura, T. Yamasaki, Y. Imai
and Y. Watanabe, J. Org. Chem., 2007, 72, 7798.
6 R. C. Miller, C. D. Miller, W. Rogers and L. A. Hamilton, J. Am. Chem.
Soc., 1957, 79, 424.
7 Topics in Phosphorus Chemistry. 31P Nuclear Magnetic Resonance,
eds. M. Grayson and E. J. Griffith, John Wiley & Sons, NewYork, 1967,
vol. 5.
2
5
Scheme 2
The prepared trimethylsilyl diphenylphosphinite 1 was sub-
jected to Arbuzov reaction with ethyl bromoacetate 6 and
(chloromethyl)diphenylphosphine oxide 7. The reactions led in
high yields to ethyl (diphenylphosphoryl)acetate 8 (dP 26.74 ppm,
lit.,8 28.9 ppm), a precursor for the synthesis of extractants for
actinides and lanthanides,9 and bis(diphenylphosphoryl)methane
9 (dP 24.64 ppm, lit.,10(a) 25.47 ppm), one of the most efficient
extractants for f-block elements (Scheme 3).10(b)
Ph2P–O–SiMe3
BrCH2CO2Et
Ph2P(O)CH2Cl
1
6
7
8 K. A. Petrov, L. I. Sivova, I. V. Smirnov and L.Yu. Kryukova, J. Gen.
Chem. USSR (Engl. Transl.), 1992, 62, 264 (Zh. Obshch. Khim., 1992,
62, 327).
O
O
O
O
Ph2P
Ph2P
PPh2
9 (a) F. Arnaud-Neu, V. Böhmer, J.-F. Dozol, C. Grüttner, R. A. Jakobi,
D. Kraft, O. Mauprivez, H. Rouquette, M.-J. Schwing-Weill, N. Simon
and W. Vogt, J. Chem. Soc., Perkin Trans. 2, 1996, 1175; (b) O. I.
Artyushin, E. V. Sharova, I. L. Odinets, S. V. Lenevich, V. P. Morgalyuk,
I. G. Tananaev, G. V. Pribylova, G. V. Myasoedova, T. A. Mastryukova
and B. F. Myasoedov, Russ. Chem. Bull., Int. Ed., 2004, 53, 2499 (Izv.
Akad. Nauk, Ser. Khim., 2004, 2394).
10 (a) S. Bittner, M. Pomerantz,Y. Assaf, P. Krief, S. Xi and M. K. Witczak,
J. Org. Chem., 1988, 53, 1; (b) V. P. Morgalyuk, N. P. Molochnikova,
G. V. Myasoedova and I. G. Tananaev, Radiochemistry, 2006, 48, 580
(Radiokhimiya, 2006, 48, 521).
OEt
8, 86%
9, 83%
Scheme 3
In conslusion, we have developed a quick convenient and
high-yield synthesis of trimethylsilyl diphenylphosphinite 1 –
a valuable reactant for the preparation of functionalized diphenyl-
phosphine oxides by Arbuzov reaction. It is also important that
initial (2-hydroxyprop-2-yl)diphenylphosphine oxide 24(a) is
stable, available, and easy for handling. The starting compound
2 can be rapidly and in high yield synthesized from Ph2PCl11(a)
or Ph2P(O)H.11(b) Reactivity of compound 2 allows us to con-
sider it as a synthetic equivalent of diphenyl phosphine oxide
(or diphenylphosphinite) anion Ph2PO–,11(a) while 2-hydroxy-
prop-2-yl moiety being a temporary protective group.
11 (a) V. P. Morgalyuk, T. V. Strelkova and E. E. Nifant’ev, Bull. Chem.
Soc. Jpn., 2012, 85, 93; (b) A. Christiansen, C. Li, M. Garland, D. Selent,
R. Ludwig, A. Spannenberg, W. Baumann, R. Franke and A. Börner, Eur.
J. Org. Chem., 2010, 2733.
Online Supplementary Materials
Supplementary data associated with this article can be found
in the online version at doi:10.1016/j.mencom.2016.09.010.
References
1 (a) P. Savignac and B. Iorga, in Modern Phosphonate Chemistry, CRC
Press, Boca Raton, 2003, pp.31–57; (b) Yu. H. Budnikova and O. G.
Sinyashin, Russ. Chem. Rev., 2015, 84, 917.
Received: 15th February 2016; Com. 16/4847
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