Diethyl Oxalate → Ethyl 2-pyridineglyoxylate

HRID 1386801Notes

Reaction equation

HRID 1386801 reaction equation
C([Li])CCC.Br[C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=1.[C:13](OCC)(=[O:19])[C:14]([O:16][CH2:17][CH3:18])=[O:15]>CCOCC>[O:19]=[C:13]([C:7]1[CH:12]=[CH:11][CH:10]=[CH:9][N:8]=1)[C:14]([O:16][CH2:17][CH3:18])=[O:15]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 79732-BromopyridineHCID 178418339Butyllithium

Product 1

HCID 9989820Ethyl 2-pyridineglyoxylate

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

A solution of n-butyllithium (100 mL, 1.6 M, 160 mmol) in hexanes was added over 2 min. to a stirred solution of 2-bromopyridine (15.0 mL, 24.9 g, 157 mmol) in 500 mL of ether cooled in a dry ice/i-PrOH bath, causing a temporary rise in temperature to 47° C. After 25 min., the solution was transferred rapidly to a stirred 0° C. solution of diethyl oxalate (75 mL, 81 g, 550 mmol) in 1000 mL of ether. After 2 h at 0° C., the mixture was washed with saturated aq. NaHCO3 (900 ml), water (900 mL), and saturated aq. NaCl (450 mL). The organic layer was dried (MgSO4), filtered, and evaporated. Distillation gave the title compound as 11.68 g of yellow liquid, B.p. 96-108° C. (0.3 mm Hg pressure). For the title compound: 1H NMR (500 MHz, CDCl3) δ 8.78 (d, J=5, 1H), 8.13 (d, J=8, 1H), 7.93 (td, J=8, 2, 1H), 7.56 (ddd, J=8, 5, 1, 11H), 4.51 (q, J=7,22H), 1.44 (t, J=7, 3H).

Workup

  1. temperaturecooled in a dry ice/i-PrOH bath
  2. customto 47° C
  3. customwas transferred rapidly to a stirred 0° C.
  4. waitAfter 2 h at 0° C.
  5. washthe mixture was washed with saturated aq. NaHCO3 (900 ml), water (900 mL), and saturated aq. NaCl (450 mL)
  6. dry with materialThe organic layer was dried (MgSO4)
  7. filtrationfiltered
  8. customevaporated
  9. distillationDistillation

Sources & evidence

ORD record
ord-d5179d9bf4174d9d869d5f827310256b
Source dataset
uspto-grants-2001_07
Patent number
US06265434B1

Reaction notes

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