Dimethyl malonate → HCID 59804279, compound

HRID 422004Notes

Reaction equation

HRID 422004 reaction equation
[H-].[Na+].[C:3]([O:10][CH3:11])(=[O:9])[CH2:4][C:5]([O:7][CH3:8])=[O:6].F[C:13]1[CH:18]=[CH:17][C:16]([NH:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)=[CH:15][C:14]=1[N+:29]([O-:31])=[O:30]>CS(C)=O>[CH3:8][O:7][C:5](=[O:6])[CH:4]([C:13]1[CH:18]=[CH:17][C:16]([NH:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)=[CH:15][C:14]=1[N+:29]([O-:31])=[O:30])[C:3]([O:10][CH3:11])=[O:9]

Participants

5

Reactant 3

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 59804338HCID 59804338, compound

Product 1

HCID 59804279HCID 59804279, compound

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent

Conditions

Temperature
60 °C

Procedure

To a suspension of 60% of NaH in mineral oil (300 mg, 7.41 mmol) in DMSO (2.5 mL) is added dimethyl malonate (851 μL, 7.41 mmol). The mixture is heated to 60° C. for 10 minutes and then cooled to ambient temperature before (4-fluoro-3-nitro-phenyl)-(3-nitro-phenyl)-amine (686 mg, 2.47 mmol) is added. The resulting mixture is heated to 60° C. for 3 hours and quenched with saturated aqueous NH4Cl solution. The mixture is extracted with EtOAc, washed with brine, dried over MgSO4, and concentrated. The crude product is purified by column chromatography (EtOAc/Hexane, gradient) to give the desired product: 1H NMR (400 MHz, CDCl3) δ. 7.94 (s, 1 H), 7.88 (d, 1 H), 7.70 (d, 1 H), 7.51-7.47 (m, 1 H), 7.44-7.40 (m, 2 H); 7.32-7.28 (m, 1H), 5.27 (s, 1H), 3.83 (s, 6H); LC-MS: 390.3 (MH+).

Workup

  1. additionis added
  2. temperatureThe resulting mixture is heated to 60° C. for 3 hours
  3. customquenched with saturated aqueous NH4Cl solution
  4. extractionThe mixture is extracted with EtOAc
  5. washwashed with brine
  6. dry with materialdried over MgSO4
  7. concentrationconcentrated
  8. customThe crude product is purified by column chromatography (EtOAc/Hexane, gradient)

Sources & evidence

ORD record
ord-0b1565cd17ab4cceb223c1e6d70c6216
Source dataset
uspto-grants-2012_01
Patent number
US08101608B2

Reaction notes

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