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Synlett 2008(19): 2938-2940  
DOI: 10.1055/s-0028-1087354
LETTER
© Georg Thieme Verlag Stuttgart ˙ New York

Synthesis of Diphenyl(nitroaryl)phosphine Oxides via Oxidative Nucleophilic Substitution of Hydrogen in Nitroarenes with Diphenylphosphine Anion

Mieczysław Mąkosza*, Maciej Paszewski, Daniel Sulikowski
Institute of Organic Chemistry, Polish Academy of Sciences, ul. Kasprzaka 44/52, 01-224 Warsaw, Poland
Fax: +48(22)6326681; e-Mail: icho-s@icho.edu.pl;
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Publication History

Received 4 September 2008
Publication Date:
12 November 2008 (online)

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Abstract

Potassium and sodium salts of diphenylphosphine add to nitroarenes in the position ortho and para to the nitro group. Subsequent oxidation of σH-adducts with potassium permanganate gave diphenyl(nitroaryl)phosphine oxides.

Key words

phosphine oxides - nucleophilic aromatic substitution - nitroarenes - carbanions

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14

Representative Procedure: To a stirred solution of nitrobenzene (246 mg, 2.00 mmol) in liquid ammonia (ca.
10 mL), at -78 ˚C was added dropwise a solution of diphenylphosphine potassium salt (0.5 M solution in THF, 2.0 mL, 1.0 mmol). After 15 min, solid potassium permanganate (396 mg, 2.00 mmol) was added. The dark mixture was stirred for further 5 min, and treated with excess of solid ammonium chloride. After evaporation of ammonia the residue was suspended in EtOAc (20 mL), stirred for 10 min and filtered through a small pad of celite. The organic phase was washed once with H2O, dried with anhyd Na2SO4 and evaporated. Column chromatography on silica gel (EtOAc) gave a mixture of o- and p-nitrophenyl diphenylphosphinoxide (178 mg, 58% yield) as an oil.

15

Selected analytical data:
Mixture 2a/2b: light orange oil. ¹H NMR (400 MHz, CDCl3; para isomer): δ = 8.30 (dd, J = 2.1, 8.8 Hz, 2 H), 7.89 (dd,
J = 11.0, 8.8 Hz, 2 H), 7.63-7.74 (m, 4H), 7.55-7.63 (m, 2H), 7.46-7.55 (m, 4 H). ¹³C NMR (100 MHz, CDCl3; para isomer): δ = 149.9 (d, J = 3 Hz), 140.3 (d, J = 98 Hz), 133.2 (d, J = 11 Hz), 132.6 (d, J = 3 Hz), 132.0 (d, J = 10 Hz), 128.8 (d, J = 12 Hz), 128.6, 123.3 (d, J = 12 Hz). ³¹P NMR (162 MHz, CDCl3): δ = 27.70 (s, para isomer), 28.39 (s, ortho isomer). MS (EI, 70 eV): m/z (%) = 323 (48) [M+], 322 (100), 277 (26), 201 (12), 77 (13).
Compound 6b: 159-161 ˚C (heptane). ¹H NMR (400 MHz, CDCl3): δ = 8.50 (m, 1 H), 8.18 (ddd, J = 8.6, 2.1, 1.4 Hz,
1 H), 7.69-7.77 (m, 4 H), 7.60-7.76 (m, 3 H), 7.45-7.59 (m, 4 H). ³¹P NMR (162 MHz, CDCl3): δ = 29.59 (s). MS (EI, 70 eV): m/z (%) = 402 (100)[M+], 356 (20), 322 (22), 201 (43), 77 (23).
Compound 8a: mp 210-211 ˚C (MeOH). ¹H NMR (400 MHz, CDCl3): δ = 8.07-8.11 (m, 2 H), 7.63-7.80 (m, 5 H), 7.54-7.62 (m, 2 H), 7.33-7.53 (m, 4 H). ¹³C NMR (100 MHz, CDCl3): δ = 149.2, 140.5 (d, J = 13 Hz), 136.3 (d,
J = 7.5 Hz), 133.0 (d, J = 2.1 Hz), 132.3 (d, J = 2.5 Hz), 131.6 (d, J = 10 Hz), 131.5, 128.6 (d, J = 13 Hz), 126.5 (d, J = 5 Hz). ³¹P NMR (162 MHz, CDCl3): δ = 29.50 (s). MS (ESI+): m/z = 358 [M + H]+.
Compound 9a: mp 162-163 ˚C (MeOH). ¹H NMR (400 MHz, CDCl3): δ = 8.12-8.30 (m, 1 H), 7.63-7.81 (m, 5 H), 7.55-7.62 (m, 3 H), 7.36-7.53 (m, 4 H). ¹³C NMR (100 MHz, CDCl3): δ = 132.6 (d, J = 3 Hz), 132.2, 131.9 (d, J = 10 Hz), 130.2, 129.0 (d, J = 13 Hz), 128.5 (d, J = 9 Hz), 128.4 (d, J = 9 Hz), 124.1 (dd, J = 8, 26 Hz), 120.3 (m), 120.0 (m). ³¹P NMR (162 MHz, CDCl3): δ = 30.01 (s). MS (ESI+): m/z = 342 [M + H]+.

17

One-Pot Procedure: To a suspension of triphenylphosphine (262 mg, 1.00 mmol) in liquid ammonia at -78 ˚C, sodium metal was added (26 mg, 1.10 mmol). The resulting mixture was stirred for 1 h and to the dark red solution nitrobenzene (369 mg, 3.00 mmol) in THF (1 mL) was added. After 15 min the mixture was treated with solid KMnO4, and after 5 min solid ammonium chloride was added. Workup as in ref. 14 gave a mixture of 2a and 2b (138 mg, 45% yield).