Triethyl phosphonoacetate → HCID 54227728, compound

HRID 1637518Notes

Reaction equation

HRID 1637518 reaction equation
[H-].[Na+].C(OP([CH2:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])(OCC)=O)C.[Si:17]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][C:29]([CH2:32][C:33](=O)[CH2:34][CH2:35][CH2:36][CH3:37])=[C:28]([O:39][CH3:40])[CH:27]=1)([C:20]([CH3:23])([CH3:22])[CH3:21])([CH3:19])[CH3:18].[Cl-].[NH4+]>CCCCCC.O1CCCC1>[Si:17]([O:24][CH2:25][C:26]1[CH:31]=[CH:30][C:29]([C:32]([CH2:33][CH2:34][CH2:35][CH2:36][CH3:37])=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13])=[C:28]([O:39][CH3:40])[CH:27]=1)([C:20]([CH3:22])([CH3:23])[CH3:21])([CH3:18])[CH3:19]

Participants

7

Reactant 4

HCID 13345Triethyl phosphonoacetateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 19348615HCID 19348615, compound

Product 1

HCID 54227728HCID 54227728, compoundYield 98.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent3×HCID 8058HexaneSolvent

Procedure

5.25 g (0.120 mol) of sodium hydride (as a 55% w/w dispersion in mineral oil) was washed with hexane and then suspended in 70 ml of tetrahydrofuran. A solution of 26.0 ml (0.131 mol) of ethyl diethylphosphonoacetate in 30 ml of tetrahydrofuran was added dropwise over a period of 40 minutes to the suspension, whilst ice-cooling, and the resulting mixture was stirred at room temperature for 10 minutes. A solution of 27.83 g (79.4 mmol) of 1-(4-t-butyldimethylsilyloxymethyl-2-methoxyphenyl)-2-oxohexane [prepared as described in step (ii) above] in 50 ml of tetrahydrofuran was then added to the mixture, which was then heated under reflux for 2.5 hours. At the end of this time, the reaction temperature was allowed to reduce to room temperature, and then a saturated aqueous solution of ammonium chloride was added to the reaction mixture. The resulting aqueous mixture was then extracted with diethyl ether. The extract was washed with water and with a saturated aqueous solution of sodium chloride, in that order, after it was dried over anhydrous magnesium sulfate, and the solvent was removed by distillation under reduced pressure. The resulting residue was purified by column chromatography through 250 g of silica gel, using a 1:9 by volume mixture of ethyl acetate and hexane as the eluent, to give 32.95 g (yield 98.7%) of the title compound as an oily substance.

Workup

  1. temperaturecooling
  2. temperaturewas then heated
  3. temperatureunder reflux for 2.5 hours
  4. customto reduce to room temperature
  5. extractionThe resulting aqueous mixture was then extracted with diethyl ether
  6. washThe extract was washed with water and with a saturated aqueous solution of sodium chloride, in that order
  7. dry with materialafter it was dried over anhydrous magnesium sulfate
  8. customthe solvent was removed by distillation under reduced pressure
  9. customThe resulting residue was purified by column chromatography through 250 g of silica gel
  10. additionby volume mixture of ethyl acetate and hexane as the eluent

Sources & evidence

ORD record
ord-628323773ef540eb8b23d9514e3bae84
Source dataset
uspto-grants-2000_03
Patent number
US06040339

Reaction notes

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