Ethyl 2,4-dioxovalerate → HCID 89649536, compound

HRID 2274563Notes

Reaction equation

HRID 2274563 reaction equation
Cl.[NH:2]([C:4]1[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][C:5]=1[C:6]([OH:8])=[O:7])[NH2:3].[CH2:16]([O:18][C:19](=[O:26])[C:20](=O)[CH2:21][C:22](=O)[CH3:23])[CH3:17]>CC(O)=O>[CH2:16]([O:18][C:19]([C:20]1[CH:21]=[C:22]([CH3:23])[N:2]([C:4]2[CH:12]=[CH:11][C:10]([N+:13]([O-:15])=[O:14])=[CH:9][C:5]=2[C:6]([OH:8])=[O:7])[N:3]=1)=[O:26])[CH3:17]

Participants

4

Reactant 2

HCID 69208Ethyl 2,4-dioxovalerateHCID 89647544HCID 89647544, compound

Product 1

HCID 89649536HCID 89649536, compoundYield 56%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of 2-hydrazinyl-5-nitrobenzoic acid hydrochloride (59.4 g, 255.1 mmol) in AcOH (500 mL) was added ethyl-2,4-dioxovalerate (31.0 g, 196.2 mmol). The reaction mixture was refluxed for 2 h. AcOH was evaporated invacuo and the residue was co-distilled with toluene (100 mL) twice. The residue was dissolved in EtOAc and washed with water until the aq. layer became neutral. The organic layer was dried over sodium sulphate and concentrated invacuo. The gummy material was triturated with diethyl ether to afford the title compound as a white solid 35 g (56%). Rf=0.30 (10% MeOH in DCM); 1H NMR (400 MHz, DMSO-d6): δ 13.90-13.60 (brs, 1H), 8.62 (d, J=2.5 Hz, 1H), 8.54 (dd, J=2.6 & 8.5 Hz, 1H), 7.90 (d, J=8.3 Hz, 1H), 6.76 (s, 1H), 4.27 (q, J=7.0 Hz, 2H), 2.19 (s, 3H), 1.28 (t, J=7.1 Hz, 3H); LC-MS: m/z 320.1 (M+H).

Workup

  1. temperatureThe reaction mixture was refluxed for 2 h
  2. customAcOH was evaporated invacuo
  3. dissolutionThe residue was dissolved in EtOAc
  4. washwashed with water until the aq. layer
  5. dry with materialThe organic layer was dried over sodium sulphate
  6. concentrationconcentrated invacuo
  7. customThe gummy material was triturated with diethyl ether

Sources & evidence

ORD record
ord-4045d2701f0e493b9df6d29c41c97fbe
Source dataset
uspto-grants-2015_09
Patent number
US09126980B2

Reaction notes

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