Diglyme → 2-(2,2-Difluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester

HRID 1901438Notes

Reaction equation

HRID 1901438 reaction equation
[O:1]([C:8]1[CH:22]=[CH:21][C:11]([O:12][CH2:13][CH2:14][O:15][C:16](=[O:20])[CH2:17]C=C)=[CH:10][CH:9]=1)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Na].Cl[C:25]([F:30])([F:29])[C:26](O)=O.[CH3:31]OCCOCCOC>>[O:1]([C:8]1[CH:22]=[CH:21][C:11]([O:12][CH2:13][CH2:14][O:15][C:16](=[O:20])[CH2:17][CH:26]2[CH2:31][C:25]2([F:30])[F:29])=[CH:10][CH:9]=1)[C:2]1[CH:3]=[CH:4][CH:5]=[CH:6][CH:7]=1

Participants

5

Reactant 4

HCID 8150Diglyme2×HCID 66154Chlorodifluoroacetic acidHCID 5360545SodiumHCID 541662683-Butenoic acid 2-(4-phenoxyphenoxy)-ethyl ester

Product 1

HCID 536827892-(2,2-Difluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester

Procedure

14.8 g of 3-butenoic acid 2-(4-phenoxyphenoxy)-ethyl ester are dissolved in 30 ml of diethylene glycol dimethyl ether (diglyme), and the solution is heated to +165° C. with stirring. A solution of 15.25 g of the sodium salt of chlorodifluoroacetic acid in 30 ml of diglyme is then added dropwise at that temperature over a period of 8 hours. The mixture is stirred for a further one hour at +165° C. and then cooled to room temperature. The reaction mixture is filtered, the residue is washed with 20 ml of diglyme and the filtrate is concentrated completely by evaporation and then taken up in 40 ml of diethyl ether, washed twice with 20 ml of water each time and dried over sodium sulfate. The solvent is concentrated by evaporation and the oily residue is then purified by column chromatography on silica gel with hexane/ethyl acetate (9:1), yielding 12.1 g of 2-(2,2-difluorocyclopropyl)-acetic acid 2-(4-phenoxyphenoxy)-ethyl ester in the form of a colourless oil having a refractive index of nD22 : 1.5309.

Workup

  1. temperaturethe solution is heated to +165° C.
  2. stirringThe mixture is stirred for a further one hour at +165° C.
  3. filtrationThe reaction mixture is filtered
  4. washthe residue is washed with 20 ml of diglyme
  5. concentrationthe filtrate is concentrated completely by evaporation
  6. washwashed twice with 20 ml of water each time
  7. dry with materialdried over sodium sulfate
  8. concentrationThe solvent is concentrated by evaporation
  9. customthe oily residue is then purified by column chromatography on silica gel with hexane/ethyl acetate (9:1)

Sources & evidence

ORD record
ord-7da417a3baea4346bc46ea23155e7ba2
Source dataset
uspto-grants-1996_11
Patent number
US05578595

Reaction notes

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