N-Fluorobenzenesulfonimide → tetraisopropyl difluoromethylenediphosphonate

HRID 1157343Notes

Reaction equation

HRID 1157343 reaction equation
[F:1][C:2]([F:23])([P:13](=[O:22])([O:18][CH:19]([CH3:21])[CH3:20])[O:14][CH:15]([CH3:17])[CH3:16])[P:3](=[O:12])([O:8][CH:9]([CH3:11])[CH3:10])[O:4][CH:5]([CH3:7])[CH3:6].C[Si]([N-][Si](C)(C)C)(C)C.[Na+].C1C=CC(S(N(S(C2C=CC=CC=2)(=O)=O)F)(=O)=O)=CC=1>C1COCC1>[F:23][C:2]([F:1])([P:3](=[O:12])([O:4][CH:5]([CH3:7])[CH3:6])[O:8][CH:9]([CH3:11])[CH3:10])[P:13](=[O:22])([O:18][CH:19]([CH3:21])[CH3:20])[O:14][CH:15]([CH3:17])[CH3:16].[F:1][CH:2]([P:3](=[O:12])([O:4][CH:5]([CH3:7])[CH3:6])[O:8][CH:9]([CH3:11])[CH3:10])[P:13](=[O:22])([O:18][CH:19]([CH3:20])[CH3:21])[O:14][CH:15]([CH3:17])[CH3:16]

Participants

6

Reactant 3

HCID 588007N-FluorobenzenesulfonimideHCID 2724254Sodium bis(trimethylsilyl)amideHCID 11717839tetraisopropyl difluoromethylenediphosphonate

Product 2

HCID 11717839tetraisopropyl difluoromethylenediphosphonateHCID 12722940Tetrapropan-2-yl (fluoromethylene)bis(phosphonate)

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a stirred solution of tetraisopropyl difluoromethylenediphosphonate (4.5 g, 13.07 mmol) in anhydrous THF (20 mL) at −78° C. under argon were added sodium bis(trimethylsilyl)amide (1.0 M in THF, 28.7 mL) and N-fluorobenzenesulfonimide (9.89 g, 31.36 mmol). The reaction mixture was stirred at −78° C. for 1 h, quenched with saturated aqueous ammonium chloride (20 mL), warmed to room temperature, diluted with ether, washed with 10% aqueous sodium bicarbonate and then with brine, dried over sodium sulfate, and concentrated. Chromatography on silica gel with 5-30% ethyl acetate in hexanes gave 2.18 g of tetraisopropyl difluoromethylenediphosphonate and 0.32 g of tetraisopropyl monofluoromethylenediphosphonate.

Workup

  1. customquenched with saturated aqueous ammonium chloride (20 mL)
  2. temperaturewarmed to room temperature
  3. additiondiluted with ether
  4. washwashed with 10% aqueous sodium bicarbonate
  5. dry with materialwith brine, dried over sodium sulfate
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-d3ba4de7ce484657ab064eed5489fba0
Source dataset
uspto-grants-2010_10
Patent number
US07807653B2

Reaction notes

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