Russian Journal of General Chemistry, Vol. 75, No. 2, 2005, pp. 313!314. Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 342!343. Original Russian Text Copyright C 2005 by Prishchenko, Livantsov, Novikova, Livantsova.
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Synthesis of Bis(trimethylsilyl) [2-(Triethoxysilyl)ethyl]phosphonite and Its Derivatives A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, and L. I. Livantsova Lomonosov Moscow State University, Moscow, Russia Received June 30, 2004
Organosilicon compounds of various structures, prepared on the basis of substituted triethoxysilane present great interest as biologically active compounds with a broad-spectrum activity [1]. In the present work we prepared functionalyzed phosphinates that contain a triethoxysilyl group along with aminomethyl fragments of various structures. Hence, bis(trimethylsiloxy)phosphine (A) easily adds to (triethoxyvinyl)silane in the presence of an AIBN catalyst under conditions of its thermolysis (1003120oC) to give phosphonite I in high yield (cf. [2]). (Me3SiO)2PH + CH2=CHSi(OEt)3 A
%$. (Me SiO) PCH CH Si(OEt) . R
3
2
2
2
3
I
Phosphonite A is a convenient synthon for preparing functionalyzed aminomethylphosphinates II which are formed in good yields in aminomethylation reactions with aminals or N-chloromethylamides. Note that the reactions with aminals proceed in the presence of a zinc chloride catalyst. I
oie 7 p 7 ! %%%$ Me SiOP 3 XCH2NR2 Me3SiX
3
CH2CH2Si(OEt)3
CH2NR2 O IIa!IIe
X = NR2 (a, b), OMe (c), Cl (d, e), NR2 = N O N (d), O (b), N(SiMe3)2 (c), (a), N N(COOEt)CH2COOMe (e).
The NMR spectra of compounds I and II contain characteristic signals of the PC1H2C2H2Si and PC5H2NC4H2 fragments. The signals of these fragments in the 1H NMR spectra of II partially or completely overlap.
Bis(trimethylsilyl) [2-(triethoxysilyl)ethyl]phosphonite (I). A mixture of 32 g of bis(trimethylsiloxy)phosphine, 19 g of (triethoxyvinyl)silane and, 0.3 g of AIBN was heated to 100oC and then, over the course of 1 h, to 120oC, after which the reaction mixture was distilled in a vacuum to give 34.8 g (87%) of phosphonite I, bp 103oC (1 mm Hg). 1H NMR spectrum, d, ppm: 1.531.6 m (C1H2), 0.730.8 m (C2H2), 0.14 s (CH3Si), 1.10 t (CH3, 3JHH 7 Hz), 3.73 q (CH2O, 3JHH 7 Hz). 13C NMR spectrum, dC, ppm: 33.91 d (C1, 1JPC 25.8 Hz), 1.09 d (C2, 2JPC 11.9 Hz), 1.53 d (CSi, 3JPC 2.8 Hz), 18.57 s (CH3), 58.48 s (CO). 31P NMR spectrum, dP, ppm: 159.34 s. Trimethylsilyl (piperidinomethyl)[2-(triethoxysilyl)ethyl]phosphinate (IIa). A mixture of 8 g of phosphonite I, 3.6 g of dipiperidinomethane, and 0.1 g of zinc chloride was heated at 03130oC for 1.5 h and then distilled to give 6.3 g (74%) of phosphinate 13 C NMR IIa, bp 146oC (1 mm Hg), n20 D 1.4502. spectrum, dC, ppm: 20,76 d (C1, JPC 93 Hz), 1.23 d (C2, 2JPC 6.6 Hz), 57.45 d (C3, 1JPC 109.6 Hz), 55.76 d (C4, 3JPC 9 Hz. 31P NMR spectrum, dP, ppm: 42.87 s. Found, %: C 47.75; H 9.39. C17H40NO5PSi2. Calculated, %: C 47.97; H 9.47. Compounds IIb!IId were obtained analogously. Trimethylsilyl (morpholinomethyl)[2-(triethoxysilyl)ethyl]phosphinate (IIb). Yield 72%, bp 13 152oC (1 mm Hg), n20 C NMR spectrum, D 1.4498. 2 1 dC, ppm: 21.03 d (C , JPC 95 Hz), 1.45 d (C2, 2JPC 6.5 Hz, 56.14 d (C3, 1JPC 111.4 Hz, 54.90 d (C4, 3JPC 8.8 Hz). 31P NMR spectrum, dP, ppm: 41.80 s. Found, %: C 44.72; H 8.81. C16H38NO6PSi2. Calculated, %: C 44.94; H 8.96. Trimethylsilyl bis(trimethylsilylaminomethyl)[2-(triethoxysilyl)ethyl]phosphinate (IIc). Yield 13 C NMR 65%, bp 147oC (2 mm Hg), n20 D 1.4458. 1 1 spectrum, dC, ppm: 22.24 d (C , JPC 85.5 Hz), 1.54 s
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(C2), 45.26 d (C3, 1JPC 102.8 Hz). 31P NMR spectrum, d, ppm: 40.78 s. Found, %: C 42.83; H 9.57. C18H48NO5PSi4. Calculated, %: C 43,08; H 9.64. Trimethylsilyl [(2-oxopyrrolidino)methyl][2-(triethoxysilyl)ethyl]phosphinate (IId). Yield 13 C NMR 73%, bp 159oC (1 mm Hg), n20 D 1.4527. 1 1 spectrum, dC, ppm: 22.84 d (C , JPC 90.7 Hz), 1.26 d (C2, 2JPC 4.2 Hz), 42.05 d (C3, 1JPC 102.3 Hz), 48.69 d (C4, 3JPC 8.1 Hz), 173.89 d (C=O, 3JPC 7.7 Hz). 31P NMR spectrum, dP, ppm: 39.09 s. Found, %: C 44.96; H 8.43. C16H30NO6PSi2. Calculated, %: C 45.15; H 8.52. Trimethylsilyl [N-(ethoxycarbonyl)-N-(methoxycarbonylmethyl)aminomethyl] [2-(triethoxysilyl)ethyl]phosphinate (IIe). Yield 69%, bp 176oC 13 (1 mm Hg), n20 D 1.4480. C NMR spectrum, dC, ppm: 1 1 22.21 d (C , JPC 89.5 Hz), 2.15 d (C2, 2JPC 3.5 Hz),
46.20 d (C3, 1JPC 105.4 Hz), 49.20 d (C4, 3JPC 7.3 Hz), 156.27 s (NC=O), 169.94 s (C=O). 31P NMR spectrum, dP, ppm: 39.97 s. Found, %: C 42.93; H 7.89. C18H40NO9PSi2. Calculated, %: C 43.10; H 8.04. The NMR spectra were measured on a Varian VXR400 spectrometer in CDCl3 against TMS (1H, 3P) and 85% H3PO4 in D2O (31P).
REFERENCES 1. Voronkov, M.G. and D’yakov, V.M., Silatrany (Silatranes), Novosibirsk: Nauka, 1978. 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, p. 156; Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Nikolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim., 2003, vol. 73, no. 3, p. 525.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY
Vol. 75
No. 2
2005
