Russian Journal of General Chemistry, Vol. 73, No. 10, 2003, pp. 1658!1660. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 10, 2003, pp. 1753!1755. Original Russian Text Copyright C 2003 by Prishchenko, Livantsov, Novikova, Livantsova, Koval’, Grigor’ev.
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Addition of Bis(trimethylsiloxy)phosphine to Indene A. A. Prishchenko, M. V. Livantsov, O. P. Novikova, L. I. Livantsova, Ya. N. Koval’, and E. V. Grigor’ev Lomonosov Moscow State University, Moscow, Russia Received December 17, 2002
Reactions of bis(trimethylsiloxy)phosphine with styrene and its heterocyclic analogs provide a convenient method of synthesis of functionalized phosphonites and their derivatives [1]. In the present work we accomplished radical addition of bis(trimethylsiloxy)phosphine to indene. The reaction proceeds regioselectively to give phosphonite I in high yield. Azobis(isobutyronitrile) acid was used as catalyst under conditions of its thermolysis (1003120oC).
oecM5
MX5 cM5 c c e o oM5 M5 eiocM5 oSQM5 . 76 (Me SiO) P R
(Me3SiO)2PH +
derivatives of new functionalized phosphinic acids containing the bicyclic indane fragments. Hence, phosphonite I undergoes facile aminomethylation when treated with aminals or N-chloromethylamides [2], giving phosphinates II in high yields.
3
2
I
Me SiOP 7776 3 XCH2NR2
2 3
IIa, IIb
1
NR2 = NMe2 (a), N(Me)CHO (b); X = Cl, NR2.
Phosphonite I was used to success for preparing
ÄÄÄÄÄÄÄÄÄÄÄÄ
Phosphonite I reacts with sulfur and benzaldehyde under mild conditions to form thiophosphinite III and phosphinate IV, respectively.
47 I 776 Me SiOP S
(Me3SiO)2P
PhCHO
3
O CH(OSiMe3)Ph
S
III
Treatment of phosphonite I and phosphinates II with a dilute solution of sodium methylate in me-
I
777776 3 MeONa, MeOH 2Me3SiOMe
IV
ÄÄÄÄÄÄÄÄÄÄÄÄ
thanol gives water-soluble sodium salts of phosphonous V and phosphinic VI acids, respectively.
NaO
777776 NaOP 3
MeONa, MeOH
P
H
O CH2NR2
I
R. = Me2(NC)C..
ÄÄÄÄÄÄÄÄÄÄÄÄ
3
Me3SiX
O
IIa, IIb
Me3SiOMe
V NR2 = NMe2 (a), N(Me)CHO (b).
Salts V and VI are colorless hygroscopic crystals. The NMR spectra of compounds I!VI contain characteristic signals of the PC1H(C2H2C3)2 substited indane and PC4H2NC5Hn fragments, whose param-
O CH2NR2 VIa, VIb
ÄÄÄÄÄÄÄÄÄÄÄÄ
eters are listed below. In the 1H NMR spectrum, these proton signals are partially or completely overlap. Note that the C2H2C3 groups in compounds II and IV which contain asymmetric phosphorus centers are
1070-3632/03/7310-1658 $25.00 C2003 MAIK
[Nauka/Interperiodica]
ADDITION OF BIS(TRIMETHYLSILOXY)PHOSPHINE TO INDENE
nonequivalent and give different signals in the 13C NMR spectra. Compounds IIb, IV, and IVb are mixtures of two stereoisomers. Bis(trimethylsilyl) (indan-2-yl)phosphonite (I). A mixture of 48 g of bis(trimethylsiloxy)phosphine, 21 g of indene, and 0.2 g of azobis(isobutyronitrile) was heated to 100oC. Then the temperature of the reaction mixture was gradually raised to 120oC over the course of 1 h. After that the reaction mixture was distilled in a vacuum to obtain 49 g of phosphonite I, yield 83%, bp 126oC (1 mm). 13C NMR spectrum, dC, ppm: 46.27 d (C1, 1JPC 20.3 Hz), 31.99 d (C2, 2JPC 19.7 Hz), 143.06 d (C3, 3JPC 5.6 Hz). dP 155.56 ppm. Trimethylsilyl (indan-2-yl)(dimethylaminomethyl)phosphinate (IIa). A mixture of 6.5 g of phosphonite I, 2.2 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 4.6 g of phosphinate IIa, yield 74%, bp 141oC (1 mm), n20 D 1.5068. 13 C NMR spectrum, dC, ppm: 35.54 d (C1, 1JPC 97.9 Hz), 31.63 and 32.23 s (C2), 140.70 d (C3, 3JPC 9.1 Hz) and 140.53 d (C3, 3JPC 9.1 Hz), 56.66 d (C4, 1 JPC 112.1 Hz), 46.51 d (C5, 3JPC 9.7 Hz) and 46.61 d (C5, 3JPC 10.5 Hz). dP 41.55 ppm. Trimethylsilyl (indan-2-yl)(N-methyl-N-formylaminomethyl)phosphinate (IIb). To a solution of 5.4 g of phosphonite I in 10 ml of methylene chloride, a solution of 1.8 g of N-chloromethyl-N-methylformamide in 5 ml of methylene chloride was added dropwise with stirring at 10oC. The solvent was then removed, and the residue was distilled in a vacuum to obtain 3.8 g of phosphinate IIb, yield 80%, bp 187oC 1 (1 mm), n20 D 1.5131. First isomer, fraction 75%. H NMR spectrum, d, ppm: 7.78 (CHO), 2.87 s (C5H3). 13 C NMR spectrum dC, ppm: 36.14 d (C1, 1JPC 96.7 Hz), 31.75 and 32.80 s (C2), 140.78 d (C3, 3JPC 8.9 Hz) and 140.93 d (C3, 3JPC 8.6 Hz), 42.50 d (C4, 1 JPC 101.0 Hz), 35.29 s (C5), 161.65 s (CO). dP 38.81 ppm. Second isomer. 1H NMR spectrum, d, ppm: 7.72 s (CHO), 2.77 s (C5H3). 13C NMR spectrum, dC, ppm: 35.91 d (C1, 1JPC 96.1 Hz), 32.04 s and 32.47 s (C2), 140.33 d (C3, 3JPC 8.8 Hz) and 140.46 d (C3, 3JPC 8.4 Hz), 46.89 d (C4, 1JPC 99.5 Hz), 35.29 s (C5), 162.12 s (CO). dP 38.26 ppm. Bis(trimethylsilyl) (indan-2-yl)thiophosphonate (III). To a solution of 4 g of phosphonite I in 10 ml of benzene, 0.4 g of sulfur was added. After exothermic reaction had been complete, the mixture was heated for 15 min on a water bath and cooled. Excess RUSSIAN JOURNAL OF GENERAL CHEMISTRY
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sulfur was filtered off, the solvent was removed, and the residue was distilled in a vacuum to obtain 4 g (91%) of thiophosphonate III, bp 142oC (1 mm), 13 1 n20 D 1.5098. C NMR spectrum, dC, ppm: 44.77 d (C , 1 JPC 117.7 Hz), 34.27 s (C2), 141.51 d (C3, 3JPC 10.6 Hz). dP 75.10 ppm. Trimethylsilyl (indan-2-yl)[phenyl(trimethylsiloxy)methyl]phosphinate (IV). To a solution of 4 g of phosphonite I in 10 ml of methylene chloride, a solution of 1.2 g of benzaldehyde in 5 ml of methylene chloride was added dropwise with stirring at 10oC. The solvent was then removed, and the residue was distilled in a vacuum to obtain 4 g of phosphinate IV, yield 83%, bp 182oC (1 mm), mp 92oC. First isomer, fraction 60%. 1H NMR spectrum, dP, ppm: 4.91 d (CHO, 2JPH 9.6 Hz). 13C NMR spectrum, dC, ppm: 34.74 d (C1, 1JPC 95.4 Hz), 32.94 and 33.39 s (C2), 141.98 d (C3, 3JPC 9.3 Hz) and 142.09 d (C3, 3 JPC 8.2 Hz), 74.09 d (CHO, 1JPC 114.9 Hz), dP 40.45 ppm. Second isomer. 1H NMR spectrum, d, ppm: 5.03 d (CHO, 2JPH 7.6 Hz). 13C NMR spectrum, dC, ppm: 35.16 d (C1, 1JPC 96.3 Hz), 33.74 s and 34.07 s (C2), 141.83 d (C3, 3JPC 9.2 Hz) and 141.98 d (C3, 3JPC 9.3 Hz), 74.04 d (CHO, 1JPC 115.3 Hz). dP 39.42 ppm. Sodium (indan-2-yl)phosphonite (V). A solution of 4.9 g of phosphonite I in 5 ml of diethyl ether was added with stirring at 10oC to a solution of 0.81 g of sodium methylate in 20 ml of methanol. The resulting mixture was heated to a boil, the solvent was removed, and the residue was kept in a vacuum (1 mm) for 1 h to obtain 3 g of salt V, yield 97%. 1H NMR spectrum, d, ppm: 6.83 d.d (PH, 1JPH 500.7 Hz, 3JHH 2.2 Hz). 13 C NMR spectrum, dC, ppm: 38.84 d (C1, 1JPC 94.5 Hz), 32.19 s (C2), 142.66 d (C3, JPC 9.1 Hz). dP 32.81 ppm, d.d (1JPH 500.7 Hz). Found, %: C 52.68; H 5.03. C9H10NaO2P. Calculated, %: C 52.95; H 4.94. Salts VIa and VIb were obtained analogously. Sodium (indan-2-yl)(dimethylaminomethyl)phosphinate (VIa). Yield 95%. 13C NMR spectrum, d, ppm: 37.71 d (C1, 1JPC 96.6 Hz), 33.08 s (C2), 142.89 d (C3, 3JPC 9.9 Hz), 57.46 d (C4, 1JPC 99.1 Hz), 46.84 d (C5, 3JPC 4.2 Hz). dP 37.83 ppm. Found, %: C 54.94; H 6.65. C12H17NNaO2P. Calculated, %: C 55.17; H 6.54. Sodium (indan-2-yl)(N-methyl-N-formylaminomethyl)phosphinate (VIb). Yield 95%. First isomer, fraction 55%. 1H NMR spectrum, d, ppm: 7.71 s No. 10
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PRISHCHENKO et al.
(CHO). 13C NMR spectrum, dC, ppm: 37.20 d (C1, 1 JPC 9.3 Hz), 43.67 d (C4, 1JPC 94.2 Hz), 36.56 s (C5), 165.35 s (CO). dP 35.86 ppm. Second isomer. 1H NMR spectrum, d, ppm: 7.91 s (CHO). 13C NMR spectrum, dC, ppm: 37.69 d (C1, 1JPC 97.6 Hz), 33.09 s (C2), 142.39 d (C3, 3JPC 8.6 Hz), 43.52 d (C4, 1 JPC 94.4 Hz), 36.62 s (C5), 164.51 s (CO). dP 36.30 ppm. Found, %: C 52.02; H 5.57. C12H15N . NaO3P. Calculated, %: C 52.37; H 5.49. The NMR spectra were recorded on a Varian VXR-
400 spectrometer in CDCl3 or D2O (salts V and VI) against TMS (1H, 13C) and 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, p. 2055; Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Pol’shchikov, D.G., and Grigor’ev, E.V., Zh. Obshch. Khim., 1999, vol. 69, no. 2, p. 346.
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