Russian Journal of General Chemistry, Vol. 73, No. 1, 2003, pp. 1553156. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 1, 2003, pp. 1633164. Original Russian Text Copyright C 2003 by Livantsov, Prishchenko, Livantsova, Nikolaev, Meleshonkova, Grigor’ev.

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Synthesis of Ferrocenyl-substituted Bis(trimethylsilyl) Alkylphosphonites and Their Derivatives M. V. Livantsov, A. A. Prishchenko, L. I. Livantsova, S. N. Nikolaev, N. N. Meleshonkova, and E. V. Grigor’ev Lomonosov Moscow State University, Moscow, Russia Received April 5, 2002

Addition of bis(trimethylsiloxy)phosphine (A) to vinyl-substituted heterocycles is a convenient synthetic route to ethylphosphonites comprising a heterocyclic fragment [1]. We have carried out the radical addition of phosphine A to vinyl- and isopropenylferrocenes, which leads to 2-ferrocenyl-substituted alkylphosphonites I in high yields. For the catalyst we used azobis(isobutyronitrile) under conditions of its thermolysis (1003120oC). Fc =

, R = H (a), Me (b). Fe

i oe eio oie

Phosphonites I are smoothly aminomethylated with bis(dimethylamino)methane in the presence of catalytic amounts of zinc chloride to form phosphinates II. CH2(NMe2)2, ZnCl2

Ia, Ib 7777776 Me3SiOP 3Me3SiNMe2

CH2CH(R)Fc

CH2NMe2 O IIa, IIb

R = H (a), Me (b).

Treatment of phosphonites I and phosphinates II with a dilute solution of sodium methylate in meMeONa, MeOH

Ia, Ib 7777776 32Me3SiOMe

NaO H

PCH2CH(R)Fc

O

IIIa, IIIb

MeONa, MeOH

IIa, IIb 7777776 NaOP 3Me3SiOMe

CH2CH(R)Fc

CH2NMe2 O IVa, IVb

R = H (a), Me (b).

thanol gave water-soluble sodium phosphonite III and and sodium phosphinate IV, respectively. Compounds I and II are cherry-red liquids, and their salts II3IV are hygroscopic yellow crystals. The 1 H NMR spectra of compounds I3IV contain characteristic signals of the PC1H2, C2H2C3, and PC5H2N . C6H3 fragments. The signals partially or completely overlap. The 1H and 13C NMR spectra of compounds I3IV contain signals of the ferrocene fragments at 434.5 and 65398 ppm, respectively. Phosphinate IIb contains asymmetric carbon and phosphorus atoms. It is a mixture of two stereoisomers whose ratio was established from the 31P NMR spectra. Bis(trimethylsilyl) [2-(ferrocenyl)ethyl]phosphonite (Ia). A mixture of 10 g of bis(trimethylsiloxy)phosphine, 4 g of ferrocene, and 0.2 g of azobis(diisobutyronitrile) was first heated to 100oC and then (over the course 1 h) to 120oC. Subsequent vacuum distillation gave 7 g of phosphonite Ia, yield 88%, bp 162oC (1 mm). 13C NMR spectrum, dC, ppm: 42.10 d (C1, JPC 24.3 Hz), 20.73 d (C2, 2JPC 16.2 Hz), 89.77 d (C3, 3JPC 12.2 Hz). dP 158.74 ppm. Bis(trimethylsilyl) [2-(ferrocenyl)propyl]phosphonite (Ib) was obtained in a similar way. Yield 85%, bp 165oC (1 mm). 1H NMR spectrum, d, ppm: 1.33 d (C4H3, 3JHH 7.2 Hz). 13C NMR spectrum, dC, ppm: 50.98 d (C1, 1JPC 27.5 Hz), 27.63 d (C2, 2JPC 14.7 Hz), 96.81 d (C3, 3JPC 7.8 Hz), 22.62 d (C4, 3JPC 8.4 Hz). dP 160.81 ppm. Trimethylsilyl (dimethylaminomethyl)[2-(ferrocenyl)ethyl]phosphinate (IIa). A mixture of 4.3 g of phosphonite Ia, 1.2 g of bis(dimethylamino)methane, and 0.1 g of zinc chloride was heated at 1103130oC for 1.5 h and then distilled to obtain 2.6 g (75%) of 13 C phosphinate IIa, bp 182oC (1 mm), n20 D 1.5435. 1 NMR spectrum, dC, ppm: 29.04 d (C , JPC 92.3 Hz), 21.40 s (C2), 87.81 d (C3, 3JPC 18.2 Hz), 57.93 d (C5,

1070-3632/03/7301-0155 $25.00 C2003 MAIK

[Nauka/Interperiodica]

156 1

JPC 113.3 Hz), 47.13 d (C6, 40.90 ppm.

LIVANTSOV et al. 3

JPC 9.8 Hz),

dP

Trimethylsilyl (dimethylaminomethyl)[2-(ferrocenyl)propyl]phosphinate (IIb) was obtained in a similar way. Yield 72%, bp 174oC (0.5 mm), n20 D 1.5422. First isomer (70%): 1H NMR spectrum, d, ppm: 1.15 d (C4H3, 3JHH 6.8 Hz); 13C NMR spectrum, 1 1 d , ppm: 36.52 d (C , JPC 92.2 Hz), 27.38 s (C2), C 3 3 95.65 d (C , JPC 15.2 Hz), 22.17 d (C4, 3JPC 3.0 Hz), 58.95 d (C5, 1JPC 9.4 Hz); dP 40.60 ppm. Second isomer: 1H NMR spectrum, d, ppm: 1.19 d (C4H3, 3 JHH 6.8 Hz); 13C NMR spectrum, dC, ppm: 36.36 d (C1, 1JPC 91.2 Hz), 27.18 s (C2), 95.53 d (C3, 3JPC 14.4 Hz), 22.26 d (C4, 3JPC 2.8 Hz), 58.90 d (C5, 1JPC 112.3 Hz), 45, 38 d (C6, 3JPC 3.8 Hz); dP 40.70 ppm. Sodium [2-(ferrocenyl)ethyl]phosphonite (IIIa). To a solution of 0.31 g of sodium methylate in 15 ml of methanol, a solution of 2.4 g of phosphonite Ia 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 obtain 1.6 g of salt IIIa. Yield 94%. 1H NMR spectrum, d, ppm: 6.95 d (PH, 1JPH 501.2 Hz). 13C NMR spectrum, dC, ppm: 33.24 d (C1, 1JPC 88.5 Hz), 21.72 (C2), 89.98 d (C3, 3JPC 18.9 Hz). dP 27.22 ppm, d (1JPH 501.2 Hz). Found,%: C 47.89; H 4.75. C12H14 . FeNaO2P. Calculated,%: C 48.04; H 4.70. Salts IIIb, IVa, and IVb were obtained in a similar way. Sodium 2-(ferrocenyl)propylphosphonite (IIIb). Yield 95%. 1H NMR spectrum, d, ppm: 7.03 d (PH, 1 JPH 502.4 Hz), 1.33 d (C4H3, 3JHH 6.8 Hz). 13C NMR spectrum, dC, ppm: 41.07 d (C1, 1JPC 89.2 Hz), 28.22 s (C2), 97.28 d (C3, 3JPC 15.0 Hz), 22.36 d (C4,

3

JPC 5.3 Hz). dP 25.69 ppm, d (1JPH 502.4 Hz). Found, %: C 49.52; H 5.22. C13H16FeNaO2P. Calculated, %: C 49.71; H 5.14. Sodium (dimethylaminomethyl)[2-(ferrocenyl)ethyl]phosphinate (IVa). Yield 95%. 13C NMR spectrum, dC, ppm: 31.59 d (C1, 1JPC 89.7 Hz), 22.49 s (C2), 90.46 d (C3, 3JPC 18.6 Hz), 58.94 d (C5, 1JPC 100.89 Hz), 47.33 d (C6, 3JPC 8.0 Hz), 58.94 d (C5, 1 JPC 100.9 Hz), 47.33 d (C6, 3JPC 8.0 Hz). dP 36.44 ppm. Found, %: C 50.28; H 6.02. C15H21Fe . NNaO2P. Calculated, %: C 50.45, H 5.93. Sodium (dimethylaminomethyl)[2-(ferrocenyl)propyl]phosphinate (IVb). Yield 93%. 1H NMR spectrum, d, ppm: 1.33 d (C4H3, 1JPC 6.8 Hz). 13C NMR spectrum, dC, ppm: 39.73 d (C1, 1JPC 88.5 Hz), 28.37 s (C2), 98.04 d (C3, 3JPC 14.9 Hz), 22.84 s (C4), 60.22 d (C5, 1JPC 101.0 Hz), 47.55 d (C6, 3JPC 8.0 Hz). dP 35.01 ppm. Found, %: C 51.49; H 6.16. C16H23 . FeNNaO2P. Calculated, %: C 51.77; H 6.24. The NMR spectra were recorded 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. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Novikova, O.P., and Grigor’ev, E.V., Zh. Obshch. Khim., 1996, vol. 66, no. 12, pp. 205532056; Livantsova, L.I., Prishchenko, A.A., Livantsov, M.V., Nikolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim., 2000, vol. 70, no. 7, pp. 122031221; Livantsova, L.I., Prishchenko, A.A., Livantsov, M.V., Nikolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim., 2000, vol. 70, no. 9, pp. 157831579.

RUSSIAN JOURNAL OF GENERAL CHEMISTRY

Vol. 73

No. 1

2003