Russian Journal of General Chemistry, Vol. 73, No. 11, 2003, pp. 1829!1831. Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 11, 2003, pp. 1930 !1932. Original Russian Text Copyright + 2003 by Prishchenko, Livantsov, Novikova, Livantsova, Koval’, Grigor’ev.
LETTERS TO THE EDITOR
Synthesis of 2-Phosphorus-Substituted Derivatives of Indan-1-carboxylic Acid A. A. Prishchenko, M. V. Livantsov, O. N. Novikova, L. I. Livantsova, Ya. N. Koval’, and E. V. Grigor’ev Moscow State University, Moscow, Russia Received March 21, 2003
Recently we have offered several convenient methods for preparing phosphorus-substituted derivatives of carboxylic acids containing various functional groups and heterocyclic fragments. These compounds are of interest as promising ligands and biologically active compounds . In this work we have studied the reactions of trimethylsilyl esters of trivalent phosphorus acids with trimethylsilyl 1H-indene-2-carboxy-
g X5 M
g c oM5
%%%%%$ (RO) P !
%%%%%$ (RO) P
o c oM5 C(OSiMe3)2
late I, yielding new 2-phosphorus-substituted derivatives of indan-1-carboxylic acid. Heating of a mixture of ester I with diethyl hydrogen phosphite and diethyl trimethylsilyl phosphite to 120oC in the presence of zinc chloride gave phosphonate IIa in high yield. Phosphonate IIb was prepared similarly. Apparently, these reactions involve intermediate formation of ketene acetals A (cf. ).
R = Et (a), Me3Si (b).
g cM5 g c oM5
Bis(trimethylsiloxy)phosphine readily adds to ester I at 1003120oC to form phosphonite III in high yield. COOSiMe3
%$ (Me SiO) P I
ÄÄÄÄÄÄÄÄÄÄÄÄ Phosphonite III is a convenient synthetic precursor of various 2-phosphorus-substituted derivatives of indan-1-carboxylic acid. For example, phosphonite III readily adds sulfur to form thiophosphonate IV and reacts with bis(dimethylamino)methane to form phosphinate V in high yield.
g oieM5 COOSiMe3
"% III %%%%$ ! Me SiOP S
1070-3632/03/7311-1829 $25.00 C2003 MAIK
PRISHCHENKO et al.
Phosphonite III readily reacts with trimethylsilyl acrylate in methylene chloride, and treatment of the intermediate adduct B with diethyl hydrogen phosphite yields phosphinate VI containing two different fragments with the carboxy groups.
Treatment of phosphonite III with a dilute solution of sodium methylate in methanol yields water-soluble disodium salt VII as white hygroscopic crystals. COONa
%%%%%%$ ! 2MeONa, MeOH 3Me3SiOMe
The NMR spectra of II!VII contain characteristic signals of the fragments of 1,2-disubstituted indan, and also of the fragments PC5H2NC6H3 and PC5H2 . C6H2CO. Their parameters are listed below. The signals of these fragments in the 1H NMR spectra partially or completely overlap. Phosphinates V and VI are mixtures of two stereoisomers. Trimethylsilyl 1H-indene-3-carboxylate I. A mixture of 41 g of 1H-indene-3-carboxylic acid prepared according to  and 100 g of bis(trimethylsilyl)amine was refluxed until the ammonia evolution ceased, and then distilled to give 54.8 g of I, yield 92%, bp 13 C NMR spectrum, dC, 148oC (8 mm), n20 D 1.5220. 1 ppm: 145.24 s (C ), 38.02 s (C2), 137.29 s (C3), 140.78 s and 143.31 s (C4), 126.44 s, 125.34 s, 123.59 s, 122.32 s (4CH from C6H4), 163.72 s (CO), 30.22 s (CSi). Diethyl 1-trimethylsiloxycarbonylindan-2-phosphonate IIa. A mixture of 4.6 g of I, 4.2 g of diethyl trimethylsilyl phosphite, 3.0 g of diethyl hydrogen phosphite, and 0.1 g of zinc chloride was heated at 120oC for 1 h and then distilled. Phosphonate IIa, 6.1 g (83%), was obtained, bp 173oC (1 mm), n20 D 1.4888. 13C NMR spectrum, dC, ppm: 36.52 d (C1, 1 JPC 147.2 Hz), 32.16 s (C2), 52.35 s (C3), 140.97 d (C4, 3JPC 10.8 Hz) and 138.75 d (C4, 3JPC 9.9 Hz), 171.29 d (CO, 3JPC 5.8 Hz). dP 28.75 ppm. Found, %: C 54.89; H 7.26. C17H27O5PSi. Calculated, %: C 55.12; H 7.35. Phosphonate IIb was prepared similarly. Bis(trimethylsilyl) 1-trimethylsiloxycarbonylindan-2-phosphonate IIb. Yield 86%, bp 165oC 13 (1 mm), n20 C NMR spectrum, dC, ppm: D 1.4771. 1 1 38.35 d (C , JPC 152.9 Hz), 32.84 s (C2), 52.94 d (C3, 2JPC 5.8 Hz), 141.44 d (C4, 3JPC 7.7 Hz) and
139.13 d (C4, 3JPC 7.4 Hz), 171.63 d (CO, 3JPC 9.3 Hz), dP 11.09 ppm. Bis(trimethylsilyl) 1-trimethylsiloxycarbonylindan-2-phosphonite III. A mixture of 28 g of bis(trimethylsiloxy)phosphine, 21 g of I, and 0.2 g of azobis(isobutyronitrile) was heated to 100oC, and in the course of 1 h the temperature was raised to 120oC. After that, the reaction mixture was distilled. Phosphonite III, 34.8 g (87%), was obtained, bp 152oC (1 mm). 13C NMR spectrum, dC, ppm: 52.72 d (C1, 1 JPC 29.5 Hz), 32.16 d (C2, 2JPC 23.9 Hz), 53.53 d (C3, 2JPC 15.3 Hz), 144.84 d (C4, 3JPC 9.4 Hz) and 141.73 d (C4, 3JPC 4.2 Hz), 172.61 s (CO). dP 159.38 ppm. O,O < -Bis(trimethylsilyl) 1-trimethylsiloxycarbonylindan-2-phosphonothioate IV. A mixture of 7 g of phosphonite III and 0.5 g of sulfur in 10 ml of benzene was heated until the sulfur dissolved, and the residue was distilled. Thiophosphonate IV, 6.2 g (83%), was obtained, bp 167oC (1 mm), n20 D 1.4971. 13 C NMR spectrum, d, ppm: 51.36 d (C1, 1JPC 120.2 Hz), 33.68 d (C2, 2JPC 5.6 Hz), 54.35 d (C3, 2 JPC 8.1 Hz), 143.21 d (C4, 3JPC 16.5 Hz) and 140.96 d (C4, 3JPC 14.9 Hz), 171.29 d (CO, 3JPC 5.9 Hz). dP 66.46 ppm. Trimethylsilyl P-dimethylaminomethyl-1-trimethylsiloxycarbonylindan-2-phosphinate V. A mixture of 5.4 g of phosphonite III, 2.8 g of bis(dimethylamino)methane, and 0.1 g of zinc chloride was heated at 110-130oC for 1.5 h and then distilled to give 4.2 g (81%) of phosphinate V, bp 186oC (1 mm), mp 67oC. First isomer, 60% content. 13C NMR spectrum, dC, ppm: 38.89 d (C1, 1JPC 96 Hz), 32.10 s (C2), 52.23 s (C3), 141.25 d (C4, 3JPC 7.1 Hz) and 139.39 d (C4, 3JPC 6.1 Hz), 57.64 d (C5, 1JPC 113.1 Hz), 47.15 d (C6, 3JPC 9.6 Hz), 171.86 s (CO). dP 41.14 ppm. Second isomer. 13C NMR spectrum, dC, ppm: 38.54 d (C1, 1JPC 96.5 Hz), 31.85 s (C2), 51.83 s (C3), 141.56 d (C4, 3JPC 6.9 Hz) and 139.14 d (C4, 3 JPC 7.1 Hz), 57.54 d (C5, 1JPC 113.6 Hz), 47.25 d (C6, 3JPC 9.8 Hz), 171.92 s (CO). dP 39.85 ppm. Trimethylsilyl P-(2-trimethylsiloxycarbonylethyl)-1-trimethylsiloxycarbonylindan-2-phosphinate VI. A solution of 2.2 g of trimethylsilyl acrylate in 5 ml of methylene chloride was added with stirring to a solution of 6.6 g of phosphonite III in 15 ml of methylene chloride. The mixture was refluxed for 30 min, and then 3.1 g of diethyl hydrogen phosphite in 5 ml of methylene chloride was added. The solvent
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SYNTHESIS OF 2-PHOSPHORUS-SUBSTITUTED DERIVATIVES
was distilled off, and the residue was heated to 100oC and then distilled to give 6.4 g (83%) of phosphinate VI, bp 197oC (1 mm), n20 D 1.4969. First isomer, 60% 13 content. C NMR spectrum, dC, ppm: 39.42 d (C1, 1 JPC 93.2 Hz), 32.13 s (C2), 52.17 s (C3), 141.26 d (C4, 3JPC 6.8 Hz) and 138.80 d (C4, 3JPC 7.1 Hz), 23.80 d (C5, 1JPC 93.6 Hz), 27.81 s (C6), 171.683 172.05 m (2CO). dP 44.21 ppm. Second isomer. 13C NMR spectrum, dC, ppm: 39.70 d (C1, 1JPC 96.6 Hz), 31.69 s (C2), 51.68 d (C3, 2JPC 6.4 Hz), 141.96 d (C4, 3 JPC 6.4 Hz) and 138.99 d (C4, 3JPC 6.4 Hz), 23.46 d (C5, 1JPC 94.1 Hz), 27.88 s (C6), 171.683172.05 m (2CO). dP 44.17 ppm. Disodium 1-carboxylatoindan-2-phosphonite VII. A solution of 7.7 g of phosphonite III in 5 ml of diethyl ether was added with stirring at 10oC to a solution of 1.9 g of sodium methylate in 30 ml of methanol. The resulting mixture was heated to reflux, the solvent was removed, and the residue was kept in a vacuum (1 mm) for 1 h to give 4.6 g of salt VII, yield 97%. 1H NMR spectrum, d, ppm: 7.12 d.d (PH, 1 JPH 527.2 Hz, 3JHH 4.0 Hz). 13C NMR spectrum, dC,
RUSSIAN JOURNAL OF GENERAL CHEMISTRY
ppm: 43.95 d (C1, 1JPC 98.9 Hz), 32.84 s (C2), 55.05 d (C3, 2JPC 9.5 Hz), 143.48 d (C4, 3JPC 13.5 Hz) and 144.78 d (C4, 3JPC 11.8 Hz), 180.44 d (CO, 3JPC 4.6 Hz). dP 31.74 ppm, d (1JPH 527.2 Hz). Found, %: C 44.28; H 3.43. C10H9Na2O4P. Calculated, %: C 44.46; H 3.36. The NMR spectra were measured on a Varian VXR-400 spectrometer in CDCl3 or D2O for salt VII against TMS (1H, 13C) and 85% H3PO4 solution in D2O (31P).
REFERENCES 1. Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., and Grigor’ev, E.V., Zh. Obshch. Khim., 1997, vol. 67, no. 11, p. 1909; Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Nikolaev, S.N., and Grigor’ev, E.V., Zh. Obshch. Khim., 2000, vol. 70, no. 6, p. 1045; Prishchenko, A.A., Livantsov, M.V., Livantsova, L.I., Nikolaev, S.N., Grigor’ev, E.V., and Novikova, O.P., Zh. Obshch. Khim., 2000, vol. 70, no. 7, p. 1222. 2. Cromwell, N.H. and Capps D.B., J. Am. Chem. Soc, 1952, vol. 74, no. 17, p. 4448.