2,3-Diethyl 2,3-pyridinedicarboxylate → Ethyl 2-formylnicotinate

HRID 1493134Notes

Reaction equation

HRID 1493134 reaction equation
C([O:3][C:4]([C:6]1[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])=[CH:10][CH:9]=[CH:8][N:7]=1)=O)C.[H-].C([Al+]CC(C)C)C(C)C>C1(C)C=CC=CC=1>[CH:4]([C:6]1[N:7]=[CH:8][CH:9]=[CH:10][C:11]=1[C:12]([O:14][CH2:15][CH3:16])=[O:13])=[O:3]

Participants

4

Reactant 2

HCID 108895172,3-Diethyl 2,3-pyridinedicarboxylateHCID 21225700Diisobutylaluminumhydride2×

Product 1

HCID 15639417Ethyl 2-formylnicotinateYield 36.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

In flame-dried glassware under N2 atmosphere, to a solution of 2,3-pyridinedicarboxylic acid diethyl ester (0.254 g, 1.14 mmol) in anhydrous toluene (5 mL) at -78° C. was added diisobutylaluminum hydride (DiBal) (1.48 mL, 1.48 mmol, 1M in toluene). After 30 minutes, additional DiBal (0.4 mL, 0.4 mmol, 1M in toluene) was added. After 15 minutes, the reaction mixture was quenched with methanol (2 mL)/saturated Na/K tartrate (40 mL) and extracted into EtOAc (3×50 mL). The combined organic extracts were washed with saturated NaHCO3 (2×50 mL), saturated brine (1×75 mL), dried over MgSO4, filtered, concentrated, and flash chromatographed (5 to 10% EtOAc/CH2Cl2 gradient) to provide 0.075 g of the title compound as a colorless oil (36.8%). 1H NMR (CDCl3, 300 MHz): δ 10.34 (s, 1H, RCHO), 8.84 (d, 1H, Arom), 8.10 (d, 1H, Arom), 7.56 (dd, 1H, Arom), 4.45 (q, 2H, OCH2), 1.40 (t, 3H, CH2CH3)

Workup

  1. waitAfter 15 minutes
  2. customthe reaction mixture was quenched with methanol (2 mL)/saturated Na/K tartrate (40 mL)
  3. extractionextracted into EtOAc (3×50 mL)
  4. washThe combined organic extracts were washed with saturated NaHCO3 (2×50 mL), saturated brine (1×75 mL)
  5. dry with materialdried over MgSO4
  6. filtrationfiltered
  7. concentrationconcentrated
  8. customflash chromatographed (5 to 10% EtOAc/CH2Cl2 gradient)

Sources & evidence

ORD record
ord-896f64e1149a41fc975752e68bec7c39
Source dataset
uspto-grants-1991_06
Patent number
US05021418

Reaction notes

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