Hexane → ((10-Undecenyl)-ethoxyphosphinyl)methylphosphonic acid dimethyl ester

HRID 2214423Notes

Reaction equation

HRID 2214423 reaction equation
C([Li])CCC.CCCCCC.[CH3:12][O:13][P:14]([CH3:18])(=[O:17])[O:15][CH3:16].[CH2:19]([P:30](Cl)(=[O:34])[O:31][CH2:32][CH3:33])[CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH:28]=[CH2:29].[Cl-].[NH4+]>O1CCCC1.C(OCC)(=O)C>[CH3:12][O:13][P:14]([CH2:18][P:30]([CH2:19][CH2:20][CH2:21][CH2:22][CH2:23][CH2:24][CH2:25][CH2:26][CH2:27][CH:28]=[CH2:29])([O:31][CH2:32][CH3:33])=[O:34])(=[O:17])[O:15][CH3:16]

Participants

8

Reactant 5

HCID 8058HexaneHCID 12958Dimethyl methylphosphonateHCID 25517Ammonium ChlorideHCID 21054114(10-Undecenyl)phosphono chloridic acid, ethyl esterHCID 178418339Butyllithium

Product 1

HCID 21054117((10-Undecenyl)-ethoxyphosphinyl)methylphosphonic acid dimethyl esterYield 78%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-50 °C

Procedure

A 2.5 M solution of n-butyllithium in hexane (9.4 mL, 23.5 mmol) was added dropwise with stirring to methylphosphonic acid dimethyl ester (2.65 g, 21.4 mmol) in 100 mL of anhydrous tetrahydrofuran at −78° C. under a nitrogen atmosphere. After 30 minutes, (10-undecenyl)phosphono chloridic acid, ethyl ester (3 g, 10.68 mrnol) was added dropwise while stirring was continued. The reaction was stirred at −78° C. for 2 hours then warmed to −50° C. and stirred for an additional 2 hours. Saturated ammonium chloride was then added to neutralize the excess base and the reaction was allowed to warm to ambient temperature. The volatiles were removed by rotary evaporation to give a viscous liquid. This liquid was diluted with ethyl acetate (200 mL) and extracted twice with water (100 mL). The organic layer was collected and dried over sodium sulfate, filtered and concentrated under rotary evaporation to give a viscous liquid. The product was then placed on a high vacuum pump to remove any remaining volatiles (3.07 g, 78% yield).

Workup

  1. stirringThe reaction was stirred at −78° C. for 2 hours
  2. stirringstirred for an additional 2 hours
  3. temperatureto warm to ambient temperature
  4. customThe volatiles were removed by rotary evaporation
  5. customto give a viscous liquid
  6. extractionextracted twice with water (100 mL)
  7. customThe organic layer was collected
  8. dry with materialdried over sodium sulfate
  9. filtrationfiltered
  10. concentrationconcentrated under rotary evaporation
  11. customto give a viscous liquid
  12. customto remove any remaining volatiles (3.07 g, 78% yield)

Sources & evidence

ORD record
ord-9c9437bef9de45efa7d1ba942e0a59ce
Source dataset
uspto-grants-2006_09
Patent number
US07109184B2

Reaction notes

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