Hexane → Methyl 4-acetyl-2,6-dichlorophenoxyacetate

HRID 266733

Reaction equation

HRID 266733 reaction equation
[H-].[Na+].CCCCCC.[CH3:9][C:10]([C:12]1[CH:17]=[C:16]([Cl:18])[C:15]([OH:19])=[C:14]([Cl:20])[CH:13]=1)=[O:11].Br[CH2:22][C:23]([O:25][CH3:26])=[O:24]>CN(C=O)C.O>[C:10]([C:12]1[CH:13]=[C:14]([Cl:20])[C:15]([O:19][CH2:22][C:23]([O:25][CH3:26])=[O:24])=[C:16]([Cl:18])[CH:17]=1)(=[O:11])[CH3:9]

Participants

7

Reactant 4

HCID 8058HexaneHCID 24758Sodium hydrideHCID 60984Methyl bromoacetateHCID 869201-(3,5-Dichloro-4-hydroxyphenyl)ethanone

Product 1

HCID 18918381Methyl 4-acetyl-2,6-dichlorophenoxyacetate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 6228DimethylformamideSolvent2×

Procedure

Sodium hydride (50% w/w dispersion in mineral oil, 1.32 g) was treated under argon with repeated washes of hexane. The oil-free residue was suspended in dry DMF (10 ml) and, with stirring and cooling (ice-bath), a solution of 3,5-dichloro-4-hydroxyacetophenone (5.13 g) in dry DMF (15 ml) was added dropwise. Stirring was continued for 30 minutes when methyl bromoacetate (3.06 ml) was added dropwise and stirring was continued for a further 18 hours at ambient temperature. The reaction mixture was added to water, the mixture was extracted twice with ethyl acetate, the organic phases dried (MgSO4), filtered and then evaporated. The residue, after recrystallisation from hexane (250 ml), gave methyl 4-acetyl-2,6-dichlorophenoxyacetate, 4.25 g, as white crystals: NMR (d6DMSO) δ 8.00 (2H, s), 4.80 (2H, s), 3.73 (3H, s), 2.59 (3H, s).

Workup

  1. temperaturecooling (ice-bath)
  2. stirringStirring
  3. stirringstirring
  4. waitwas continued for a further 18 hours at ambient temperature
  5. extractionthe mixture was extracted twice with ethyl acetate
  6. dry with materialthe organic phases dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. customThe residue, after recrystallisation from hexane (250 ml)

Sources & evidence

ORD record
ord-dd65fcb68f874f9ca6a9419c49377ebe
Source dataset
uspto-grants-1997_07
Patent number
US05652242

Linked notes

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