Diethyl Oxalate → HCID 57433879, compound

HRID 887197Notes

Reaction equation

HRID 887197 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([Li])CCC.[C:17](OCC)(=[O:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19].[NH4+].[Cl-]>C1COCC1>[CH:7]1[C:8]2[C:3](=[C:2]([C:17](=[O:23])[C:18]([O:20][CH2:21][CH3:22])=[O:19])[CH:11]=[CH:10][CH:9]=2)[CH:4]=[CH:5][N:6]=1

Participants

6

Reactant 4

HCID 7268Diethyl OxalateHCID 25517Ammonium ChlorideHCID 7364875-BromoisoquinolineHCID 178418339Butyllithium

Product 1

HCID 57433879HCID 57433879, compoundYield 35.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

The product from Example 57A (11.80 g, 56.6 mmol) in THF (200 mL) at −78° C. was treated with n-butyllithium (30 mL, 75.0 mmol, 2.5M in hexanes) dropwise. After 30 minutes, the mixture was treated with diethyl oxalate (25.0 mL, 184 mmol). After 20 minutes, the solution was allowed to warm to room temperature and was treated with saturated NH4Cl (150 mL). The mixture was concentrated under reduced pressure. The residue was treated with dichloromethane (100 mL) filtered, and the filtrate concentrated under reduced pressure. The residue was purified by column chromatography (20% ethyl acetate/hexanes) to provide the title compound as light brown oil (4.57 g, 35%). MS (ESI+) m/z 248 (100), 230 (M+H)+, (ESI−) m/z 200 (M−Et)−; 1H NMR (DMSO-d6, 300 MHz) rotomers δ 1.26 (t, J 7.1, 0.6H), 1.37 (t, J 7.1, 2.4H), 4.21 (q, J 7.1, 0.4H), 4.47 (q, J 7.1, 1.6H), 7.89 (t, J 7.5, 1H), 8.41 (dd, J 1.0, 7.5, 1H), 8.57 (d, J 8.1, 1H), 8.64 (d, J 5.7, 1H), 8.73 (d, J 6.3, 1H), 9.50 (s, 1H).

Workup

  1. waitAfter 20 minutes
  2. concentrationThe mixture was concentrated under reduced pressure
  3. additionThe residue was treated with dichloromethane (100 mL)
  4. filtrationfiltered
  5. concentrationthe filtrate concentrated under reduced pressure
  6. customThe residue was purified by column chromatography (20% ethyl acetate/hexanes)

Sources & evidence

ORD record
ord-6006b7e2d6294ad38148d620a1c87c91
Source dataset
uspto-grants-2012_08
Patent number
US08247413B2

Reaction notes

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