ISSN 1070-3632, Russian Journal of General Chemistry, 2006, Vol. 76, No. 8, pp. 1338!1339. C Pleiades Publishing, Inc., 2006. Original Russian Text C L.M. Burnaeva, V.F. Mironov, L.M. Abdrakhmanova, G.A. Ivkova, A.A. Balandina, Sh.K. Latypov, I.V. Konovalova, A.N. Pudovik, 2006, published in Zhurnal Obshchei Khimii, 2006, Vol. 76, No. 8, pp. 1394 !1395.
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Cyclic P(III)-Phosphorylated Derivatives of Pamoic Acid: Reaction of 4,4 -Methylenebis(2-ethoxynaphtho[2,3-d]1,3,2-dioxaphosphorin-4-one) with Hexafluoroacetone <
L. M. Burnaevaa, V. F. Mironovb, L. M. Abdrakhmanovaa, G. A. Ivkovaa, K A. A. Balandinab, Sh. K. Latypovb, I. V. Konovalovaa, and A. N. Pudovika a Kazan
State University, Kazan, Tatarstan, Russia Arbuzov Institute of Organic and Physical Chemistry, Kazan Scientific Center, Russian Academy of Sciences, ul. Arbuzova 8, Kazan, Tatarstan, 420088 Russia
b
Received March 6, 2006
DOI: 10.1134/S1070363206080330 We found previously [1, 2] that the reaction of 2-R-benzo-1,3,2-dioxaphosphorin-4-ones with hexafluoroacetone yields six-membered heterocyclic compounds, 2-R-4,4-bis(trifluoromethyl)benzo[d]-1,3,2dioxaphosphepin-2,5-diones, which can be further used in the synthesis of fluorinated functional ketones [3, 4]. In this study we attempted to apply this approach to relatively complicated phosphorylated derivatives of pamoic acid [5] such as 4,4 -methylene-
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bis(2-ethoxynaphtho[2,3-d]-1,3,2-dioxaphosphorin-4one) I. We prepared I previously by the reaction of ethyl phosphorodichloridite with pamoic acid trimethylsilyl derivative II. Using dynamic 31P {1H} NMR method, we found that keeping a mixture of II and excess ethyl phosphorodichloridite for 3 h at 20 C leads to the formation of an intermediate exhibiting a signal at P 152.7 ppm in the 31P NMR spectrum. In 7 days, this signal transforms into the signals of two d
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1338
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CYCLIC P(III)-PHOSPHORYLATED DERIVATIVES OF PAMOIC ACID
diastereomers of I at P 123.59 and 122.57 ppm. The intermediate has probably acyclic structure III. d
Compound I reacts with hexafluoroacetone under mild conditions (a mixture of CH2Cl2 and CCl4, 40 C) to form 11,11 -methylenebis{4,4-bis(trifluoromethyl)-2-ethoxynaphtho[2,3-d]-1,3,2-dioxaphosphepin-2,5-dione} IV (two diastereomers). Its structure was proved by NMR spectroscopy using COSY 1H 1 H, HSQS, and HMBC techniques. In the HMBC spectrum, the cross peaks were recorded between 11CH2 protons and carbon nuclei C11 and C10a; between H7, H9 and C10a; and between H7 and C6, which allowed complete assignment of the 13C NMR signals. 3
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Thus, tre reactions of phosphorylated pamoic acid derivatives of type I with hexafluoroacetone allows preparation of compounds containing two dioxaphosphepin rings. Compound IV. To a mixture of 9.95 g of I, 25 ml of CCl4, and 15 ml of CH2Cl2 ( 40 C), we condensed 6.16 g of hexafluoroacetone in a flow of dry argon. The reaction mixture was allowed to warm to 20 C over a period of 5 h and then was kept for 24 h at 20 C. The precipitate of IV was filtered off and dried in a vacuum; yield 87%, mp 335 C. IR spectrum, , cm31: 1712 (C=O), 1600 1620 (C=Car), 1240 (P=O), 1048 (POC). 1H NMR spectrum (600 MHz, CDCl3), , ppm (J, Hz): 1.01 t.d (CH3, 3JHCCH 7.1), 3.87 d.d.q (OCHA, 2JHCH 10.0, 3JPOCH 10.0, 3JHCCH 7.1), 3.97 m (OCHB, 2JHCH 10.0, 3JPOCH 7.9, 3JHCCH 7.1), 4.92 m (CH2), 7.98 s (H6), 7.79 br.d (H7, 3JH8CCH7 8.1), 7.34 br.d.d (H8, 3JH7CCH8 8.1, 3JH9CCH8 7.1), 7.42 d.d.d (H9, 3 JH10CCH9 8.6, 3JH8CCH9 7.1, 4JH7CCCH9 1.3), 7.98 d (H10, 3JH9CCH10 8.6). 13C NMR spectrum (150.9 MHz, CDCl3 + 20% acetone-d6), , ppm (J, Hz) (in parentheses, the signal shape in the 13C {1H} spectrum): 82.61 sept.d (sept.d) (C4, 2JFCC4 29.6, 2 JPOC4 6.5), 186.08 d (s) (C5, 3JHC6CC5 5.0), 126.81 s (s) (C5a), 132.81 d.d (br.s) (C6, 1JHC6 166.7, 3 JHC7CC6 5.1), 130.46 m (s) (C6a, 3JHC8CC6a 7.2, 3 JHC10CC6a 7.2, 2JHCC6a 1.6, 2JHCC6a 1.2), 130.37 d.d.d (s) (C7, 1JHC7 162.2, 3JHCCC7 7.0, 3JHCCC7 5.3), 126.69 d.d (br.s) (C8, 1JHC8 163.4, 3JHC10CC8 8.1), 130.14 d.d (br.s) (C9, 1JHC9 161.9, 3JHC7CC9 8.3), 123.89 d.d 3
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1339
(br.s) (C10, 1JHC10 161.1, 3JHC8CC10 7.1), 135.08 m (s) (C10a), 127.01 d (d) (C11, 3JPOCC11 7.8), 140.93 d.d.t (d) (C11a, 3JHC6CC11a 9.4 10.4, 2JPOC11a 6.6, 3 JHC15CC11a 5.3), 67.13 t.d.q (d) (C12, 1JHC12 151.1, 2 JPOC12 5.7, 2JHC13C12 4.3), 15.06 q.d.t (d) (C13, 1 JHC13 128.1, 3JPOCC13 6.5, 2JHC12C13 2.5), 23.09 t (s) (C15, 1JHC15 130.5). 19F NMR spectrum (282.4 MHz, CDCl3), F, ppm (J, Hz): 71.73 and 73.32 (A3B3 spectrum, 4JFCCF 9.4), 71.40 and 73.49 (A3B3 spectrum, 4JFCCF 9.2). 31P NMR spectrum (121.42 MHz, CDCl3): P 12.1 and 12.3 ppm. Found, %: C 45.40; H 2.67. C33H22F12O10P2. Calculated, %: C 45.62; H 2.53. 3
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The IR spectrum was measured on a Bruker Vector22 spectrophotometer from a mull in mineral oil. The NMR spectra were recorded on Varian Unity-300 (31P, 31 P {1H}) and Bruker Avance-600 (1H, 13C, 13C 1 { H}, COSY 1H 1H, HSQS, and HMBC) instruments. 3
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ACKNOWLEDGMENTS
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY
Vol. 76
This study was financially supported by the programs Russian Universities Basic Research (project no. UR 05.01.006) and Support of Leading Scientific Schools of the Russian Federation (project no. 750.2003.3). [
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REFERENCES 1. Mironov, V.F., Konovalova, I.V., Mavleev, R.A., Mukhtarov, A.Sh., Ofitserov, E.N., and Pudovik, A.N., Zh. Obshch. Khim., 1991, vol. 61, no. 10, p. 2150. 2. Mironov, V.F., Burnaeva, L.A., Konovalova, I.V., Khlopushina, G.A., and Zyablikova, T.A., Zh. Obshch. Khim., 1995, vol. 65, no. 12, p. 1986. 3. Mironov, V.F., Konovalova, I.V., and Burnaeva, L.M., Zh. Org. Khim., 1996, vol. 32, no. 3, p. 403. 4. Mironov, V.F., Burnaeva, L.M., Litvinov, I.A., Kotorova, Yu.Yu., Dobrynin, A.B., Musin, R.Z., and Konovalova, I.V., Izv. Ross. Akad. Nauk, Ser. Khim., 2004, no. 8, p. 1640. 5. Fei, Z., Slawin, A.M.Z., and Woollins, J.D., Polyhedron, 2001, vol. 20, p. 3355.
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