Acetic Acid → HCID 13273328, compound

HRID 1285406Notes

Reaction equation

HRID 1285406 reaction equation
C([Li])CCC.[CH3:6][O:7][P:8]([CH3:12])(=[O:11])[O:9][CH3:10].C([O:15][C:16](=O)[C:17]([CH3:24])([CH3:23])[CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])C.C(O)(=O)C>CCCCCC.O1CCCC1>[CH3:6][O:7][P:8]([CH2:12][C:16]([C:17]([CH3:24])([CH3:23])[CH2:18][CH:19]=[C:20]([CH3:22])[CH3:21])=[O:15])(=[O:11])[O:9][CH3:10]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 12958Dimethyl methylphosphonateHCID 550341HCID 550341, compoundHCID 178418339Butyllithium

Product 1

HCID 13273328HCID 13273328, compoundYield 65.7%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolvent

Procedure

Under argon at -60° C., 49.5 ml of a 2.02N butyllithium solution in hexane was added dropwise to a solution of 13 g of methanephosphonic acid dimethyl ester in 160 ml of absolute tetrahydrofuran. After 15 minutes, a solution of 9.2 g of 2,2,5-trimethyl-4-hexenoic acid ethyl ester in 25 ml of absolute tetrahydrofuran was added dropwise thereto. After 2 hours at -60° C., the reaction mixture was allowed to warm up to room temperature within one hour, combined with 5.72 ml of glacial acetic acid, and then concentrated under vauum. The residue, a white, gel-like mass, was distributed in a two-phase mixture of 35 ml of water and 165 ml of ether. The organic phase was dried over magnesium sulfate and concentrated on a forced circulation evaporator. After removing the volatile byproducts by distillation under 0.1 torr and at 60° C., the residue was purified by column chromatography on silica gel with hexane/50-100% ethyl acetate as the mobile phase, thus obtaining 8.6 g of the title compound.

Workup

  1. waitAfter 2 hours at -60° C.
  2. concentrationconcentrated under vauum
  3. additionThe residue, a white, gel-like mass, was distributed in a two-phase mixture of 35 ml of water and 165 ml of ether
  4. dry with materialThe organic phase was dried over magnesium sulfate
  5. concentrationconcentrated on a forced circulation evaporator
  6. customAfter removing the volatile byproducts
  7. distillationby distillation under 0.1 torr
  8. customat 60° C., the residue was purified by column chromatography on silica gel with hexane/50-100% ethyl acetate as the mobile phase

Sources & evidence

ORD record
ord-5aa7fd4351ad45f48ba649048fa09489
Source dataset
uspto-grants-1986_01
Patent number
US04567195

Reaction notes

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