Dimethyl malonate → 2-[2-Nitro-3-(3-nitro-phenylamino)-phenyl]-malonic acid dimethyl ester

HRID 422016Notes

Reaction equation

HRID 422016 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[C:14]([N+:29]([O-:31])=[O:30])=[C:15]([NH:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)[CH:16]=[CH:17][CH:18]=1.[NH4+].[Cl-]>CS(C)=O>[CH3:8][O:7][C:5](=[O:6])[CH:4]([C:13]1[CH:18]=[CH:17][CH:16]=[C:15]([NH:19][C:20]2[CH:25]=[CH:24][CH:23]=[C:22]([N+:26]([O-:28])=[O:27])[CH:21]=2)[C:14]=1[N+:29]([O-:31])=[O:30])[C:3]([O:10][CH3:11])=[O:9]

Participants

6

Reactant 4

HCID 7943Dimethyl malonateHCID 24758Sodium hydrideHCID 25517Ammonium ChlorideHCID 59804315(3-Fluoro-2-nitro-phenyl)-(3-nitro-phenyl)-amine

Product 1

HCID 866231752-[2-Nitro-3-(3-nitro-phenylamino)-phenyl]-malonic acid dimethyl ester

Reagents, catalysts & solvents 1

HCID 679Dimethyl SulfoxideSolvent2×

Procedure

To a suspension of NaH (60% dispersion in mineral oil, 0.26 g, 11 mmol) in DMSO (30 ml) is added dimethyl malonate (1.43 g, 11 mmol) slowly. The reaction is stirred at room temperature for 1 hour. After that, a solution of (3-fluoro-2-nitro-phenyl)-(3-nitro-phenyl)-amine (1.0 g, 3.6 mmol) in DMSO (5 ml) is added. The reaction is brought to 80° C. and stirred for 20 hours. It is poured into saturated NH4Cl and extracted with ethyl acetate (30 ml×3). The organic layers are combined, washed with water, brine and dried with Na2SO4. The desired compound is obtained after purification of the residue by flash column chromatography (silica gel, eluted by hexa-nes-ethyl acetate): LC-MS: 390.0 (MH+),

Workup

  1. customis brought to 80° C.
  2. stirringstirred for 20 hours
  3. extractionextracted with ethyl acetate (30 ml×3)
  4. washwashed with water, brine
  5. dry with materialdried with Na2SO4

Sources & evidence

ORD record
ord-4a5f5d18ba69451184fc11a4f0efc89a
Source dataset
uspto-grants-2012_01
Patent number
US08101608B2

Reaction notes

Loading…