Sodium Iodide → 5,5-Bis{bis[(propan-2-yl)oxy]phosphoryl}pentanoic acid

HRID 1737285Notes

Reaction equation

HRID 1737285 reaction equation
[H-].[Na+].[CH2:3]([P:14](=[O:23])([O:19][CH:20]([CH3:22])[CH3:21])[O:15][CH:16]([CH3:18])[CH3:17])[P:4](=[O:13])([O:9][CH:10]([CH3:12])[CH3:11])[O:5][CH:6]([CH3:8])[CH3:7].Br[CH:25]([CH2:31][CH3:32])[C:26]([O:28]CC)=[O:27].[I-].[Na+]>CN(C)C=O.O>[CH:20]([O:19][P:14]([O:15][CH:16]([CH3:18])[CH3:17])([CH:3]([P:4]([O:9][CH:10]([CH3:11])[CH3:12])([O:5][CH:6]([CH3:8])[CH3:7])=[O:13])[CH2:32][CH2:31][CH2:25][C:26]([OH:28])=[O:27])=[O:23])([CH3:22])[CH3:21]

Participants

7

Reactant 4

HCID 5238Sodium IodideHCID 24758Sodium hydrideHCID 74266Tetraisopropyl methylenediphosphonateHCID 79039Butanoic acid, 2-bromo-, ethyl ester

Product 1

HCID 218420025,5-Bis{bis[(propan-2-yl)oxy]phosphoryl}pentanoic acidYield 8.7%

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent

Procedure

Under a nitrogen atmosphere, 60% sodium hydride (2.56 g) was suspended in dry N,N-dimethylformamide (20 ml), and tetraisopropyl methylenebisphosphonate (20.0 g) was added dropwise thereto at room temperature. After stirring for 10 minutes, ethyl bromobutyrate (8.4 ml) was added dropwise thereto and the resulting mixture was stirred at 100° C. for 1 hour. Then, sodium iodide (0.85 g) was added thereto and stirred for 4 hours. Water was added thereto, followed by extraction (twice) with ethyl acetate, and the organic layer was dried over anhydrous magnesium sulfate and concentrated under reduced pressure. The residue was dissolved in methanol (50 ml), followed by adding thereto a 2N aqueous sodium hydroxide solution (10 ml), and the resulting mixture was stirred with heating under reflux for 3 hours. The mixture was acidified with 1N hydrochloric acid and extracted with ethyl acetate, and the organic layer was washed with a saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure, and then the residue was purified by a silica gel column chromatography to obtain 5,5-bis(diisopropoxyphosphinoyl)valeric acid (1.88 g, yield 8.7%). 1H-NMR (CDCl3) δ: ppm; 1.34 (12H, d, J=6.3 Hz), 1.34 (12H, d, J=5.9 Hz), 1.8-2.4 (7H, m), 4.7-4.9 (4H, m).

Workup

  1. customat room temperature
  2. stirringthe resulting mixture was stirred at 100° C. for 1 hour
  3. stirringstirred for 4 hours
  4. extractionfollowed by extraction (twice) with ethyl acetate
  5. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe residue was dissolved in methanol (50 ml)
  8. additionby adding
  9. stirringa 2N aqueous sodium hydroxide solution (10 ml), and the resulting mixture was stirred
  10. temperaturewith heating
  11. temperatureunder reflux for 3 hours
  12. extractionextracted with ethyl acetate
  13. washthe organic layer was washed with a saturated aqueous sodium chloride solution
  14. dry with materialdried over anhydrous magnesium sulfate
  15. concentrationconcentrated under reduced pressure
  16. customthe residue was purified by a silica gel column chromatography

Sources & evidence

ORD record
ord-7d0be34f2b234eb1ab5f8bb0dc07e111
Source dataset
uspto-grants-1999_10
Patent number
US05962438

Reaction notes

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