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Synlett 2011(12): 1735-1739  
DOI: 10.1055/s-0030-1260935
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

An Effective Borate-Mediated Approach to 1-Trifluoromethyl-1-hydroxy-3-ketophosphonates, Phosphinates, and Phosphine Oxides

Dmitrii L. Chizhov*a, Vera Vogelb, Sergey N. Tverdomedb, Valery N. Charushina, Gerd-Volker Röschenthalerb
a I. Postovsky Institute of Organic Synthesis, Ural Branch of the Russian Academy of Sciences, 620990 Ekaterinburg, GSP-147, Russia
Fax: +7(343)3693058; e-Mail: dlchizhov@ios.uran.ru;
b School of Engineering and Science, Jacobs University Bremen, P.O. Box 750561, 28725 Bremen, Germany
Further Information

Publication History

Received 27 January 2011
Publication Date:
05 July 2011 (online)

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Abstract

Ethyl 1-trifluoromethyl-1-hydroxy-3-oxo-phosphonates, the related (methyl)phosphinates and (phenyl)phosphinates, and phosphine oxides were obtained in good yield via direct phosphonylation of acyltrifluoroacetones with diethyl phosphite, ethyl (methyl)phosphonite, ethyl (phenyl)phosphonite, and diphenyl-phosphine oxide in the presence of triethyl borate. The subsequent dehydration of the selected phosphonates and phosphinates proceeds smoothly affording previously unknown diethyl 1,2-unsaturated 1-trifluoromethyl-3-oxophosphonates, ethyl 1-trifluoro-methyl-3-oxo(methyl)-, and ethyl 1-trifluoromethyl-3-oxo(phenyl) phosphinates in good yields.

Key words

acyltrifluoroacetones - phosphonylation - triethyl borate - fluorinated phosphonate - fluorinated phosphinate - fluorinated phosphine oxides

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13

Typical Procedure for the Preparation of Compounds 4-7 A mixture of diketone 3 (10.0 mmol), phosphorus reagent [11.0 mmol in the case of diethyl phosphite or ethyl(methyl)phosphonite, 15 mmol in the case of ethyl(phenyl)phosphonite, or 20 mmol in the case of diphenylphosphine oxide], and triethylborate (1.60 g, 11.0 mmol in the case of phosphite and phosphonites or 2.92 g, 20.0 mmol in the case of diphenylphosphine oxide) was refluxed in MeCN (20 mL) for the respective time (Table  [¹] ). All volatile materials were removed in vacuo, and the residue was dissolved in Et2O (30 mL). The ether solution was washed with H2O (10 mL) and 10% solution of Na2CO3 (3 × 10 mL). For compounds 6 and 7 a sat. solution of NaHCO3 was used. Et2O was removed, the crude product was dissolved in CHCl3 (10 mL) and filtered through a layer of silica (3 sm). The solvent was evaporated, and the residue was dried in vacuo for 12 h. For compounds 6 and 7, the products were purified by column chromatography (EtOAc-hexane = 1:2).
Data for Diethyl 1-Hydroxy-3-(4-nitrophenyl)-3-oxo-1-(trifluoromethyl)propylphosphonate (4b)
Yellowish viscous oil. ¹H NMR (200 MHz, CDCl3): δ = 1.23 (t, 3 H, Me, J = 7.1 Hz), 1.27 (t, 3 H, Me, J = 7.1 Hz), 3.21 (dd, 1 H, J Ha-Hb = 16.1 Hz, J Ha-P = 18.6 Hz, CHH), 3.82 (dd, 1 H, J Ha-Hb = 16.1 Hz, J Hb-P = 7.3 Hz, CHH), 4.10-4.36 (m, 4 H, 2 OCH2), 6.74 (d, 1 H, J H-P = 8.3 Hz, OH) 7.61-7.66 (m, 2 H, Ar), 7.88-7.93 (m, 2 H, Ar). ¹9F NMR (188 MHz, CDCl3, C6F6): δ = 88.96 (d, J F-P = 5.2 Hz, CF3). ³¹P-¹H decoupled (81 MHz, CDCl3, 85% H3PO4): δ = 16.68 (q, J P-F = 5.2 Hz). ¹³C NMR (50 MHz, CDCl3) δ = 16.13 (d, ³ J C-P = 5.2 Hz, Me), 38.64 (s, CH2), 63.58 (d, ² J C-P = 7.4 Hz, OCH2), 63.63 (d, ² J C-P = 7.4 Hz, OCH2), 75.58 (dq, ¹ J C-P = 164.6 Hz, ² J C-F = 29.0 Hz), 124.41 (qd, CF3, ¹ J C-F = 285.4 Hz, ² J C-P = 12.6 Hz), 124.42, (CH, Ar), 130.87 (CH, Ar), 143.03 (Ar), 150.70 (Ar), 195.94 (d, ³ J C-P = 8.5 Hz, C=O). Anal. Calcd for C14H17NPF3O7: C, 42.12; H, 4.29; F, 14.28. Found: C, 42.31; H, 4.17; F, 14.42.

18

General Procedure for the Preparation of Compounds 8-10
To a vigorously stirred solution of phosphonate 4 or phosphinate 5 or 6 (5.0 mmol) and dry pyridine (0.79 g, 10 mmol) in dry CH2Cl2 (20 mL) a solution of TFAA (2.10 g, 10 mmol) in dry CH2Cl2 (20 mL) was added dropwise at 0 ˚C. The reaction mixture was stirred for 4 h at the same temperature, warmed to r.t., washed with cold H2O (ca. 5 ˚C, 3 × 10 mL), and filtered through layer of silica (4 sm). The solvent was evaporated and residue was dried in vacuo for 12 h.
Data for Diethyl 3-(4-Nitrophenyl)-3-oxo-1-(trifluoromethyl)prop-1-enylphosphonate (8b) Yellow viscous oil; E/Z = 10:1.
Compound ( Z )-8b: ¹H NMR (200 MHz, CDCl3): δ = 1.27 (t, 6 H, 2 Me, J = 7.1 Hz), 4.01-4.17 (m, 4 H, 2 OCH2), 7.57 (dq, 1 H, J H-P = 39.0 Hz, J H-F = 1.5 Hz, =CH), 8.02-8.06 (m, 2 H, Ar), 8.31-8.36 (m, 2 H, Ar). ¹9F NMR (188 MHz, CDCl3, C6F6): δ = 99.27 (s). ³¹P-¹H coupled (81 MHz, CDCl3, 85% H3PO4): δ = 6.67 (dm, J P-H = 39.0 Hz). ³¹P-¹H decoupled (81 MHz, CDCl3, 85% H3PO4): δ = 6.67 (q,
J P-F = 2.5 Hz). ¹³C NMR (50 MHz, CDCl3): δ = 16.00 (d, ³ J C-P = 7.1 Hz, Me), 63.80 (d, ² J C-P = 5.7 Hz, OCH2), 121.65 (qd, CF3, ¹ J C-F = 275.5 Hz, ² J C-P = 15.5 Hz), 124.06 (CH, Ar), 129.00 (dq, ¹ J C-P = 182.3 Hz, ² J C-F = 32.5 Hz), 129.82, (CH, Ar), 139.48 (Ar), 147.39 (m, =CH), 150.82 (Ar), 190.20 (d, ³ J C-P = 7.1 Hz, C=O).
Compound ( E )-8b: ¹H NMR (200 MHz, CDCl3): δ = 1.41 (t, 6 H, 2 Me, J = 7.1 Hz), 4.19-4.35 (m, 4 H, 2 OCH2), 7.77 (d, 1 H, J H-P = 24.0 Hz, =CH), 8.02-8.06 (m, 2 H, Ar), 8.31-8.36 (m, 2 H, Ar). ¹9F NMR (188 MHz, CDCl3, C6F6): δ = 104.36 (d, J F-P = 5.5 Hz). ³¹P-¹H decoupled (81 MHz, CDCl3, 85% H3PO4): δ = 9.06 (q, J P-F = 5.2 Hz). ¹³C NMR (50 MHz, CDCl3): δ = 16.20 (d, ³ J C-P = 7.0 Hz, Me), 64.09 (d, ² J C-P = 5.7 Hz, OCH2), 124.26 (CH, Ar), 130.04, (CH, Ar), 148.66 (m, =CH). Signals of carbon without hydrogen were not found. Anal. Calcd for C14H15NPF3O6: C, 44.11; H, 3.97; F, 14.95. Found: C, 44.03; H, 3.75; F, 15.10.