Hydrochloric Acid → Methyl [2-(5-acetylamino-2-chloro-4-fluorophenoxy)phenoxy]acetate

HRID 433721Notes

Reaction equation

HRID 433721 reaction equation
[ClH:1].[C:2]([NH:5][C:6]1[C:7]([F:26])=[CH:8][C:9](N)=[C:10]([CH:24]=1)[O:11][C:12]1[CH:23]=[CH:22][CH:21]=[CH:20][C:13]=1[O:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])(=[O:4])[CH3:3].N([O-])=O.[Na+]>[Cu]Cl.O.COC(C)(C)C>[C:2]([NH:5][C:6]1[C:7]([F:26])=[CH:8][C:9]([Cl:1])=[C:10]([CH:24]=1)[O:11][C:12]1[CH:23]=[CH:22][CH:21]=[CH:20][C:13]=1[O:14][CH2:15][C:16]([O:18][CH3:19])=[O:17])(=[O:4])[CH3:3]

Participants

7

Reactant 3

HCID 313Hydrochloric AcidHCID 21053882Methyl [2-(5-acetylamino-2-amino-4-fluorophenoxy)phenoxy]acetateHCID 23668193Sodium Nitrite

Product 1

HCID 21053881Methyl [2-(5-acetylamino-2-chloro-4-fluorophenoxy)phenoxy]acetate

Reagents, catalysts & solvents 3

HCID 62652Cuprous chlorideCatalystHCID 962WaterSolvent2×HCID 15413tert-Butyl methyl etherSolvent

Procedure

To 30 ml of conc. hydrochloric acid was added 2.0 g of methyl [2-(5-acetylamino-2-amino-4-fluorophenoxy)phenoxy]acetate, and the mixture was stirred for 1 hour at room temperature. Thereafter, a mixture of 0.42 g of sodium nitrite and 3 ml of water was added under ice cool. The mixture was stirred for 1 hour under the same condition, then, 40 ml of t-butyl methyl ether was added, then, 0.85 g of copper (I) chloride was added. The mixture was stirred for 30 minutes, then, water was added to this, and extracted with t-butyl methyl ether, and the organic layer was washed with water, dried over magnesium sulfate and concentrated, and the resulted residue was purified by column chromatography (eluent: hexane/ethyl acetate=2/1) to obtain 0.52 g of methyl [2-(5-acetylamino-2-chloro-4-fluorophenoxy)phenoxy]acetate.

Workup

  1. additionwas added under ice
  2. temperaturecool
  3. stirringThe mixture was stirred for 1 hour under the same condition
  4. stirringThe mixture was stirred for 30 minutes
  5. extractionextracted with t-butyl methyl ether
  6. washthe organic layer was washed with water
  7. dry with materialdried over magnesium sulfate
  8. concentrationconcentrated
  9. customthe resulted residue was purified by column chromatography (eluent: hexane/ethyl acetate=2/1)

Sources & evidence

ORD record
ord-cc1a95b3f43740108dcba52943297eb0
Source dataset
uspto-grants-2003_12
Patent number
US06667413B2

Reaction notes

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