Dimethyl oxalate → HCID 67338224, compound

HRID 751500Notes

Reaction equation

HRID 751500 reaction equation
Br[C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][N:6]=[CH:7]2.[C:12](OC)(=[O:17])[C:13]([O:15][CH3:16])=[O:14]>C1COCC1>[CH3:16][O:15][C:13](=[O:14])[C:12]([C:2]1[CH:11]=[CH:10][CH:9]=[C:8]2[C:3]=1[CH:4]=[CH:5][N:6]=[CH:7]2)=[O:17]

Participants

4

Reactant 2

HCID 11120Dimethyl oxalateHCID 7364875-Bromoisoquinoline

Product 1

HCID 67338224HCID 67338224, compoundYield 59%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

Tert-BuLi (1.7 M pentane, 27.2 mL, 46.3 mmol) is added to dry THF (195 mL) at −78° C., after few minutes, a solution of 5-bromo-isoquinoline (6.42 g, 30.86 mmol) in THF (5 mL) is added via syringe dropwise. The resulting solution is allowed to stir at −78° C. for 45 minutes, then dimethyl oxalate (11 g, 93 mmol) is added in one portion. After 30 min at −78° C., the reaction is quenched using saturated ammonium chloride solution, diluted with 200 mL EtOAc, and then the TB is removed by rotovap. The residue is diluted with saturated ammonium chloride solution extracted with EtOAc (2×200 mL). The organic layers are combined and washed with 1×75 mL water and 1×75 mL brine, dried over anhydrous sodium sulfate, then concentrated. The material is then purified using flash column chromatography, 20% EtOAC/Hexanes, to yield 3.91 g, 59% of isoquinolin-5-yloxoacetic acid methyl ester. MS (ES, m/z): (M+30 1) 216.1

Workup

  1. waitAfter 30 min at −78° C.
  2. customthe reaction is quenched
  3. additiondiluted with 200 mL EtOAc
  4. customthe TB is removed by rotovap
  5. additionThe residue is diluted with saturated ammonium chloride solution
  6. extractionextracted with EtOAc (2×200 mL)
  7. washwashed with 1×75 mL water and 1×75 mL brine
  8. dry with materialdried over anhydrous sodium sulfate
  9. concentrationconcentrated
  10. customThe material is then purified

Sources & evidence

ORD record
ord-732a4f599bac439185a56f1d0ed0a949
Source dataset
uspto-grants-2008_07
Patent number
US07405305B2

Reaction notes

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