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

Abstract

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

phosphine oxides - nucleophilic aromatic substitution - nitroarenes - carbanions

References and Notes

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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]⁺.

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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).