Acetic Acid → Dimethyl (3-methylidene-2-oxoheptyl)phosphonate

HRID 1284313Notes

Reaction equation

HRID 1284313 reaction equation
C([Li])CCC.[CH3:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9].[CH2:13]([C:17](=[CH2:23])[C:18](OCC)=[O:19])[CH2:14][CH2:15][CH3:16].C(O)(=O)C>C(OCC)C.O1CCCC1>[O:19]=[C:18]([C:17](=[CH2:23])[CH2:13][CH2:14][CH2:15][CH3:16])[CH2:6][P:7](=[O:12])([O:10][CH3:11])[O:8][CH3:9]

Participants

7

Reactant 4

HCID 176Acetic AcidHCID 12958Dimethyl methylphosphonateHCID 3014221Hexanoic acid, 2-methylene-, ethyl ester2×HCID 178418339Butyllithium

Product 1

HCID 21440328Dimethyl (3-methylidene-2-oxoheptyl)phosphonateYield 69%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

A 2N solution (400 ml.) of n-butyllithium in diethyl ether was added dropwise to a solution of dimethyl methylphosphonate (110 g.) in pure anhydrous tetrahydrofuran (700 ml.) with stirring under nitrogen, while the reaction temperature was kept within the range of -50° to -60°C. After 10 minutes, a solution of ethyl 2-n-butylacrylate (prepared as described in (1) above; 60 g.) in tetrahydrofuran (150 ml.) was added dropwise to the reaction mixture at -65° to -70°C. and stirred for 4 hours at the same temperature. The reaction mixture was further stirred overnight at 0°C, acidified with acetic acid and concentrated under reduced pressure. Diethyl ether and water were added to the residue in order to remove the water soluble materials. The ethereal solution was dried over magnesium sulphate and concentrated. The residue was distilled under reduced pressure to give pure dimethyl 2-oxo-3-methylene-n-heptylphosphonate (67 g; 69%), having the following physical characteristics:-

Workup

  1. customwas kept within the range of -50° to -60°C
  2. stirringstirred for 4 hours at the same temperature
  3. waitThe reaction mixture was further stirred overnight at 0°C
  4. concentrationconcentrated under reduced pressure
  5. additionDiethyl ether and water were added to the residue in order
  6. customto remove the water soluble materials
  7. dry with materialThe ethereal solution was dried over magnesium sulphate
  8. concentrationconcentrated
  9. distillationThe residue was distilled under reduced pressure

Sources & evidence

ORD record
ord-bc832bbb7fcf4b3d8b1eaa29ee5c1f28
Source dataset
uspto-grants-1976_08
Patent number
US03978229

Reaction notes

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