Diethyl Oxalate → Ethyl 2-(5-bromo-2-(methoxymethoxy)phenyl)-2-oxoacetate

HRID 455563

Reaction equation

HRID 455563 reaction equation
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[CH:4][C:3]=1[O:9][CH2:10][O:11][CH3:12].[Li]CCCC.[C:18](OCC)(=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20]>CCOCC>[Br:8][C:6]1[CH:5]=[CH:4][C:3]([O:9][CH2:10][O:11][CH3:12])=[C:2]([C:18](=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH:7]=1

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 105658332,4-Dibromo-1-(methoxymethoxy)benzeneHCID 178418339Butyllithium

Product 1

HCID 57475646Ethyl 2-(5-bromo-2-(methoxymethoxy)phenyl)-2-oxoacetateYield 112.8%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of 2,4-dibromo-1-(methoxymethoxy)benzene (40.5 g, 137 mmol) in Et2O (140 mL) was cooled to −78° C. and treated with n-BuLi (2.5M in hexanes; 60.2 mL, 151 mmol) under nitrogen atmosphere. After 30 minutes a solution of diethyl oxalate (27.9 mL, 205 mmol) in Et2O (20 mL) was added dropwise. The reaction mixture was stirred for 45 minutes at that temperature then quenched cold with saturated ammonium chloride solution. The mixture was partitioned between Et2O and water. The organic phase was separated, washed with water, brine, then dried over MgSO4. The solvent was removed under reduced pressure to afford 49 g of ethyl 2-(5-bromo-2-(methoxymethoxy)phenyl)-2-oxoacetate, which was used in the next step without further purification.

Workup

  1. customthen quenched cold with saturated ammonium chloride solution
  2. customThe mixture was partitioned between Et2O and water
  3. customThe organic phase was separated
  4. washwashed with water, brine
  5. dry with materialdried over MgSO4
  6. customThe solvent was removed under reduced pressure

Sources & evidence

ORD record
ord-c8a2fe41913f4aea80c8466dc2776192
Source dataset
uspto-grants-2013_07
Patent number
US08497264B2

Linked notes

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