Diethyl Oxalate → Ethyl 2-methoxybenzoylformate

HRID 31354

Reaction equation

HRID 31354 reaction equation
Br[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[O:8][CH3:9].C([Li])CCC.[C:15](OCC)(=[O:21])[C:16]([O:18][CH2:19][CH3:20])=[O:17].[NH4+].[Cl-]>CCOCC.CCCCC>[CH3:9][O:8][C:3]1[CH:4]=[CH:5][CH:6]=[CH:7][C:2]=1[C:15](=[O:21])[C:16]([O:18][CH2:19][CH3:20])=[O:17]

Participants

7

Reactant 4

HCID 7268Diethyl OxalateHCID 113582-BromoanisoleHCID 25517Ammonium ChlorideHCID 178418339Butyllithium

Product 1

HCID 15579652Ethyl 2-methoxybenzoylformate

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 8003PentaneSolvent

Procedure

A solution of 27 g of 1-bromo-2-methoxybenzene in 270 ml of ether is cooled to −70° C. under an argon atmosphere, 90 ml of a 1.6 M solution of n-butyl-lithium in pentane are added dropwise and the mixture is then left stirring for 45 minutes. 78 ml of diethyl oxalate are added rapidly and the mixture is left stirring, while allowing the temperature to return to RT. After stirring for 1 hour at RT, saturated NH4Cl solution is added to the mixture, the phases are separated after settling has taken place, the aqueous phase is extracted with ether, the combined organic phases are washed with water and then with saturated NaCl solution and dried over Na2SO4, and the solvents are evaporated off under vacuum. The excess diethyl oxalate is removed by distillation under vacuum (b.p.=87° C. at 2 000 Pa). The resulting product is chromatographed on silica gel, eluting with a DCM/hexane mixture (50/50; v/v) and then with DCM. The product obtained is purified by distillation under vacuum. 13 g of the expected product are obtained; b.p.=110° C. at 3 Pa.

Workup

  1. waitthe mixture is then left
  2. waitthe mixture is left
  3. stirringstirring
  4. customto return to RT
  5. stirringAfter stirring for 1 hour at RT
  6. customthe phases are separated after settling
  7. extractionthe aqueous phase is extracted with ether
  8. washthe combined organic phases are washed with water
  9. dry with materialwith saturated NaCl solution and dried over Na2SO4
  10. customthe solvents are evaporated off under vacuum
  11. customThe excess diethyl oxalate is removed by distillation under vacuum (b.p.=87° C. at 2 000 Pa)
  12. customThe resulting product is chromatographed on silica gel
  13. washeluting with a DCM/hexane mixture (50/50; v/v)
  14. customThe product obtained
  15. distillationis purified by distillation under vacuum

Sources & evidence

ORD record
ord-e1496e4568d7464da8f731298c452447
Source dataset
uspto-grants-2008_09
Patent number
US07425566B2

Linked notes

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