Diethyl Oxalate → HCID 86619021, compound

HRID 1821812Notes

Reaction equation

HRID 1821812 reaction equation
[O-]CC.[K+:4].[C:5]([O:12][CH2:13][CH3:14])(=[O:11])[C:6]([O:8]CC)=O.[CH2:15]([N:22]([CH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=1)[C:23]1[CH:28]=[C:27]([CH3:29])[C:26]([N+:30]([O-:32])=[O:31])=[CH:25][N:24]=1)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1>C(OCC)C>[CH2:33]([N:22]([CH2:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1)[C:23]1[CH:28]=[C:27](/[CH:29]=[C:6](\[O-:8])/[C:5]([O:12][CH2:13][CH3:14])=[O:11])[C:26]([N+:30]([O-:32])=[O:31])=[CH:25][N:24]=1)[C:34]1[CH:35]=[CH:36][CH:37]=[CH:38][CH:39]=1.[K+:4]

Participants

5

Reactant 3

HCID 7268Diethyl OxalateHCID 23670592Potassium ethoxideHCID 68981936HCID 68981936, compound

Product 1

HCID 86619021HCID 86619021, compoundYield 76.6%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

To a suspension of potassium ethoxide (2.21 g, 26.3 mmol) in diethyl ether (20 mL) was added diethyl oxalate (3.57 mL, 26.3 mmol) under a nitrogen atmosphere. The reaction exhibited a slight exotherm and the reaction mixture was stirred for 20 min. The heterogeneous mixture became a homogeneous orange solution and then became a heterogeneous thick slurry and the stirring was ceased. In a separate container 2-(dibenzylamino)-5-nitro-4-methylpyridine (8.76 g, 26.3 mmol) was diluted with diethyl ether (14.3 mL) to give a suspension. The suspension was added to the slurry obtained above. The mixture was manually stirred using a glass rod, then sonicated for 20 min resulting in a thick black heterogeneous solution. The reaction mixture was allowed to stand under a nitrogen atmosphere overnight. The resulting solid was collected by filtration and rinsed with diethyl ether to give potassium (1Z)-1-[2-(dibenzylamino)-5-nitropyridin-4-yl]-3-ethoxy-3-oxoprop-1-en-2-olate (9.5 g, 76%) as a deep red solid: 1H NMR (300 MHz, CD3OD) δ1.17 (3H, t, J=7.0 Hz), 3.58 (2H, q, J=6.9 Hz), 4.82 (4H, s), 7.22-7.32 (11H, m), 8.74 (1H, s), 8.80 (1H, s).

Workup

  1. customto give a suspension
  2. additionThe suspension was added to the slurry
  3. customobtained above
  4. stirringThe mixture was manually stirred
  5. customsonicated for 20 min
  6. customresulting in a thick black heterogeneous solution
  7. waitto stand under a nitrogen atmosphere overnight
  8. filtrationThe resulting solid was collected by filtration
  9. washrinsed with diethyl ether

Sources & evidence

ORD record
ord-2aa14c16f0a549a18107d05620f9cfd9
Source dataset
uspto-grants-2009_10
Patent number
US07608627B2

Reaction notes

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