CID 406 → HCID 21321719, compound

HRID 261926Notes

Reaction equation

HRID 261926 reaction equation
[CH3:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4].P(=O)([O-])[O-].C([Li])CCC.[CH:17]1([CH2:20][CH2:21][CH2:22][CH2:23][C:24](OC)=[O:25])[CH2:19][CH2:18]1>O1CCCC1.CCCCCC.C(O)(=O)C>[O:25]=[C:24]([CH2:23][CH2:22][CH2:21][CH2:20][CH:17]1[CH2:19][CH2:18]1)[CH2:1][P:2](=[O:7])([O:5][CH3:6])[O:3][CH3:4]

Participants

8

Reactant 4

HCID 406CID 406HCID 12958Dimethyl methylphosphonateHCID 21321726HCID 21321726, compoundHCID 178418339Butyllithium

Product 1

HCID 21321719HCID 21321719, compound

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent

Procedure

A solution of 49.6 g (0.40 mole) dimethyl methylphosphonate (Aldrich) in 500 ml dry tetrahydrofuran is cooled to -78° in a dry nitrogen atmosphere. To the stirred phosphonate solution is added 188 ml of 2.34 M n-butyllithium in hexane solution (Alfa Inorganics, Inc.) dropwise over a period of 18 minutes at such a rate that the reaction temperature never rises above -65°. After an additional 5 minutes stirring at -78°,25.6 g (0.20 mole) methyl 5-cyclopropylvalerate is added dropwise at a rate that keeps the reaction temperature less than -70° (20 minutes). After 1.0 hour at -78° the reaction mixture is allowed to warm to ambient temperature, neutralized with 25 ml acetic acid and rotary evaporated to a white gel. The gelatinous material is taken up in 75 ml water, the aqueous phase extracted with 100 ml portions of chloroform (3x), the cmbined organic extracts are backwashed (50 cc H2O), dried (MgSO4), and concentrated (water aspirator) to a crude residue and distilled to give dimethyl 2-oxo-6-cyclopropylhexylphosphonate.

Workup

  1. customthe reaction temperature less than -70° (20 minutes)
  2. waitAfter 1.0 hour at -78° the reaction mixture is allowed
  3. customrotary evaporated to a white gel
  4. extractionthe aqueous phase extracted with 100 ml portions of chloroform (3x)
  5. dry with materialdried (MgSO4)
  6. concentrationconcentrated (water aspirator) to a crude residue
  7. distillationdistilled

Sources & evidence

ORD record
ord-73bf69a5cd8340bb97783f8d6e6cc696
Source dataset
uspto-grants-1979_05
Patent number
US04152527

Reaction notes

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