Tetrahydrofuran → Dimethyl (3,3-dimethyl-2-oxoheptyl)phosphonate

HRID 1076051Notes

Reaction equation

HRID 1076051 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].C1COCC1.[CH3:18][C:19]([CH3:29])([CH2:25][CH2:26][CH2:27][CH3:28])[C:20](OCC)=[O:21]>C(O)(=O)C>[O:21]=[C:20]([C:19]([CH3:29])([CH3:18])[CH2:25][CH2:26][CH2:27][CH3:28])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9]

Participants

6

Reactant 4

HCID 8028Tetrahydrofuran2×HCID 12958Dimethyl methylphosphonateHCID 3024116Ethyl dimethylhexanoateHCID 178418339Butyllithium

Product 1

HCID 13018035Dimethyl (3,3-dimethyl-2-oxoheptyl)phosphonate

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

n-Butyllithium (400 ml.) is slowly added to a solution of dimethyl methylphosphonate (73.7 g.) in 1.3 l. of THF at about -66° C. To the mixture is added a solution of ethyl 2,2-dimethylhexanoate (53 g.) in 150 ml. of THF, and the resulting mixture is stirred at -70° C. for 2 hrs. Then, 46 ml. of acetic acid is added, and the mixture is concentrated under reduced pressure. The residue is mixed with portions of dichloromethane (about 1.2 l.) and water (about 150 ml.), shaken, and separated. The organic phase is dried over magnesium sulfate and concentrated. Distillation yields the title compound, 41.6 g., b.p. 117°-120° C./1 mm.

Workup

  1. customat about -66° C
  2. concentrationthe mixture is concentrated under reduced pressure
  3. additionThe residue is mixed with portions of dichloromethane (about 1.2 l.) and water (about 150 ml.)
  4. customseparated
  5. dry with materialThe organic phase is dried over magnesium sulfate
  6. concentrationconcentrated
  7. distillationDistillation

Sources & evidence

ORD record
ord-689f80c79a3449afa29fe9979b52ef32
Source dataset
uspto-grants-1976_05
Patent number
US03954833

Reaction notes

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