Methyl phenylacetate → Dimethyl-2-oxo-3-phenylpropyl phosphonate

HRID 437202Notes

Reaction equation

HRID 437202 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].O1CCCC1.C([Li])CCC.[C:18]1([CH2:24][C:25](OC)=[O:26])[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1>CCCCCC.C(O)(=O)C>[O:26]=[C:25]([CH2:24][C:18]1[CH:23]=[CH:22][CH:21]=[CH:20][CH:19]=1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Participants

7

Reactant 4

HCID 7559Methyl phenylacetateHCID 8028Tetrahydrofuran2×HCID 12958Dimethyl methylphosphonateHCID 178418339Butyllithium

Product 1

HCID 12805884Dimethyl-2-oxo-3-phenylpropyl phosphonate

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 8058HexaneSolvent

Conditions

Temperature
25 °C

Procedure

A solution of dimethyl methylphosphonate (62 g.) in 400 ml. of tetrahydrofuran at -74° C. is treated by slow addition of 316 ml. of 1.6 M n-butyllithium in hexane, while maintaining the temperature below -62° C. A solution of phenylacetic acid, methyl ester (37.5 g.) in 100 ml. of tetrahydrofuran is added while maintaining the temperature below -60° C. The mixture is stirred at that temperature for 3 hr. and then allowed to warm to about 25° C. Acetic acid (30 g.) is added and the resulting precipitate removed by filtration. The filtrate is concentrated, taken up in diethyl ether, washed with water and brine, dried over magnesium sulfate and concentrated to the product, 38.74 g. The product is further distilled 140°-155° C./0.4 mm. to yield 19.5 g. of the title compound.

Workup

  1. temperaturewhile maintaining the temperature below -60° C
  2. customthe resulting precipitate removed by filtration
  3. concentrationThe filtrate is concentrated
  4. washwashed with water and brine
  5. dry with materialdried over magnesium sulfate
  6. concentrationconcentrated to the product, 38.74 g
  7. distillationThe product is further distilled 140°-155° C./0.4 mm
  8. customto yield 19.5 g

Sources & evidence

ORD record
ord-1faadfcc09fa4e97b4d72eddb572653d
Source dataset
uspto-grants-1977_06
Patent number
US04029814

Reaction notes

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