Ethyl 2,4-dioxovalerate → HCID 89649760, compound

HRID 2274571Notes

Reaction equation

HRID 2274571 reaction equation
Cl.[Br:2][C:3]1[CH:4]=[CH:5][C:6]([NH:12][NH2:13])=[C:7]([CH:11]=1)[C:8]([OH:10])=[O:9].[CH2:14]([O:16][C:17](=[O:24])[C:18](=O)[CH2:19][C:20](=O)[CH3:21])[CH3:15]>CC(O)=O>[Br:2][C:3]1[CH:4]=[CH:5][C:6]([N:12]2[C:20]([CH3:21])=[CH:19][C:18]([C:17]([O:16][CH2:14][CH3:15])=[O:24])=[N:13]2)=[C:7]([CH:11]=1)[C:8]([OH:10])=[O:9]

Participants

4

Reactant 2

HCID 69208Ethyl 2,4-dioxovalerateHCID 53418411HCID 53418411, compound

Product 1

HCID 89649760HCID 89649760, compoundYield 100.4%

Reagents, catalysts & solvents 1

HCID 176Acetic AcidSolvent

Procedure

To a solution of 5-bromo-2-hydrazinylbenzoic acid hydrochloride (60.0 g, 225.6 mmol) in AcOH (600 mL) was added ethyl-2,4-dioxovalerate (35.67 g, 225.6 mmol) followed by refluxing for 3 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 brown colored oil 80 g (100%), which was used without further purification for the next step. Rf=0.23 (10% MeOH in DCM); 1H NMR (400 MHz, DMSO-d6): δ 13.80-12.80 (brs, 1H), 8.08 (d, J=1.9 Hz, 1H), 7.96 (dd, J=2.4&8.3 Hz, 1H), 7.53 (d, J=8.3 Hz, 1H), 6.70 (s, 1H), 4.26 (q, J=7.2 Hz, 2H), 2.13 (s, 3H), 1.28 (t, J=7.1 Hz, 3H); ES-MS: m/z 353.1 (M+H).

Workup

  1. temperatureby refluxing for 3 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-cec4a5e32d69495e8ae0a92c63b1b18f
Source dataset
uspto-grants-2015_09
Patent number
US09126980B2

Reaction notes

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