Russian Journal of General Chemistry, Vol. 73, No. 1, 2003, pp. 1533154. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 1, 2003, pp. 1613162. Original Russian Text Copyright C 2003 by Prishchenko, Livantsov, Livantsova, Nikolaev, Grigor’ev.
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Addition of Bis(trimethylsiloxy)phosphine to Triethyl(vinyl)germane A. A. Prishchenko, M. V. Livantsov, L. I. Livantsova, S. N. Nikolaev, and E. V. Grigor’ev
eio i oe 77
Lomonosov Moscow State University, Moscow, Russia Received April 5, 2002
Functionalized derivatives of organophosphorus acids containing organogermanium fragments present interest as promising ligands and biologically active compounds [1]. We report here the radical addition of bis(trimethylsiloxy)phosphine to triethyl(vinyl)germane, that provides phosphonite I in high yield (cf. [2]).
MeONa, MeOH
7776
i oe 77
(R2N)2CH2, ZnCl2
I 7777776 Me3SiOP 3
Me3SiNR2
R2N =
O
N (a), O
CH2CH2GeEt3 CH2NR2 N (b).
Treatment of phosphonite I and phosphinates II with a dilute solution of sodium methylate in methanol results in formation of water-soluble sodium phosphonite III and sodium phosphinate I, respectively. Salts III and IV are white hygroscopic crystals. The 1H NMR spectra of compounds I3IV contain characteristic signals of the PC1H2C2H2Ge and PC3H2 . NC4H3 fragments, whose parameters are listed below. The signals partially or completely overlap. Bis(trimethylsilyl) [2-(triethylgermyl)ethyl]-
PCH2CH2GeEt3
O
MeONa, MeOH
IIa, IIb 777776 NaOP
R2N =
III
CH2CH2GeEt3
CH2NR2 O IVa, IVb
Me3SiOMe
3
(Me3SiO)2PCH2CH2GeEt3 I
Phosphonite I was successfully used by us for preparing new functionalized organophosphorus acids containing stable triethylgermyl groups. Hence, phosphonite I is easily aminomethylated with bis(dialkylamino)methanes at 130oC in the presence of zinc chloride to give phosphinates IIa and IIb in high yield.
H
2Me3SiOMe
3
(Me3SiO)2PH + CH2=CHGeEt3 Me2(NC)C.
NaO
I 777776
N (a), O
N (b).
phosphonite (I). A mixture of 31 g of bis(trimethylsiloxy)phosphine, 13.2 g of triethyl(vinyl)germane, and 0.2 g of azobis(isobutyronitrile) was first heated to 100oC and then (over the course of 1 h) to 120oC. Subsequent distillation gave 21.9 g (78%) of phosphonite I, bp 113oC (1 mm). 13C NMR spectrum, dC, ppm: 35.67 d (C1, 1JPC 25.7 Hz), 3.70 s (C2). dP 158.30 ppm. Trimethylsilyl (N-piperidinomethyl)[2-(triethylgermyl)ethyl]phosphinate (IIa). A mixture of 4 g of phosphonite I, 1.9 g of bis((N-piperidino)methane, and 0.1 g of zinc chloride was heated at 1103130oC for 1.5 h and then distilled to obtain 3 g (67%) of 13 C phosphinate IIa, bp 160oC (1 mm), n20 D 1.4755. 1 1 NMR spectrum, dC, ppm: 23.36 d (C , JPC 89.7 Hz), 2.71 d (C2, 2JPC 8.3 Hz), 56.59 d (C3, 1JPC 111.1 Hz), 56.16 d (C4, 3JPC 8.9 Hz). dP 43.63 ppm. Trimethylsilyl (N-morpholinomethyl)[2-(triethylgermyl)ethyl]phosphinate (IIb) was obtained in a similar way. Yield 68%, bp 152oC (1 mm), n20 D 1.4785. 13C NMR spectrum, dC, ppm: 23.38 d (C1, 1 JPC 90.7 Hz), 1.94 d (C2, 2JPC 8.2 Hz), 1.94 d (C2, 2 JPC 8.2 Hz), 56.03 d (C3, 1JPC 110.8 Hz), 55.05 d (C4, 3 JPC 9.1 Hz). dP 42.35 ppm.
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PRISHCHENKO et al.
Sodium [2-(triethylgermyl)ethyl]phosphonite (III). To a solution of 0.55 g of sodium methylate in 30 ml of methanol, a solution of 4 g of phosphonite I in 5 ml of diethyl ether was added with stirring at 10oC. The reaction mixture was heated to boiling, the solvent was distilled off, and the residue was subjected to a vacuum (1 mm) for 1 h to give 2.7 g (97%) of salt III. 1H NMR spectrum, d, ppm: 6.82 d.t (PH, 1 JPH 497.2 Hz, 3JHH 2.0 Hz). 13C NMR spectrum, dC, ppm: 26.95 d (C1, 1JPC 87.2 Hz), 2.18 d (C2, 2JPC 5.9 Hz). dP 32.13 ppm, d, 1JPH 497.5 Hz. Found, %: C 34.72; H 7.49. C8H20GeNaO2P. Calculated, %: C 34.97; H 7.37. Sodium (N-piperidinomethyl[2-(triethylgermyl)ethyl]phosphinate (IVa) was obtained in a similar way. Yield 95%. 13C NMR spectrum, dC, ppm: 26.69 d (C1, 1JPC 87.5 Hz), 4.26 d (C2, 2JPC 5.4 Hz), 57.77 d (C3, 1JPC 98.3 Hz), 56.58 d (C4, 3JPC 7.1 Hz). dP 38.62 ppm. Found, %: C 45.02; H 8.52. C14H31 . GeNNaO2P. Calculated, %: C 45.21; H 8.40. Sodium (N-morpholinomethyl)[2-(triethylger-
myl)ethyl]phosphinate (IVb). Yield 96%. 13C NMR spectrum, dC, ppm: 25.53 d (C1, 1JPC 88.2 Hz), 3.45 d (C2, 2JPC 5.2 Hz), 57.38 d (C3, 1JPC 102.2 Hz), 55.58 d (C4, 3JPC 8.1 Hz). dP 38.82 ppm. Found, %: C 41.64; H 7.81. C13H29GeNNaO3P. Calculated, %: C 41.76; H 7.88. The NMR spectra were obtained on a Varian VXR400 spectrometer in CDCl3 or D2O (salts III and IV) against TMS (1H, 13C) or 85% H3PO4 in D2O (31P).
REFERENCES 1. Lutsenko, I.F., Pure Appl. Chem., 1972, vol. 30, ' pp. 4093425; Lesbre, M., Mazerolles, P., and Satge, J., The Organic Compounds of Germanium, London: Academic, 1971. Translated under the title Organicheskie soedineniya germaniya, Moscow: Mir, 1974, pp. 3893408. 2. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Pol’shchikov, D.G., Nikolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim., 1999, vol. 69, no. 1, pp. 1563157.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY
Vol. 73
No. 1
2003
