Sodium hydride → 2-(3,5-Difluoro-2-nitro-phenyl)-malonic acid di-tert-butyl ester

HRID 970349Notes

Reaction equation

HRID 970349 reaction equation
[H-].[Na+].[C:3]([O:13][C:14]([CH3:17])([CH3:16])[CH3:15])(=[O:12])[CH2:4][C:5]([O:7][C:8]([CH3:11])([CH3:10])[CH3:9])=[O:6].F[C:19]1[CH:24]=[C:23]([F:25])[CH:22]=[C:21]([F:26])[C:20]=1[N+:27]([O-:29])=[O:28]>CN(C=O)C>[C:14]([O:13][C:3](=[O:12])[CH:4]([C:19]1[CH:24]=[C:23]([F:25])[CH:22]=[C:21]([F:26])[C:20]=1[N+:27]([O-:29])=[O:28])[C:5]([O:7][C:8]([CH3:9])([CH3:10])[CH3:11])=[O:6])([CH3:17])([CH3:16])[CH3:15]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 675671,3,5-Trifluoro-2-nitrobenzeneHCID 68324Di-tert-butyl malonate

Product 1

HCID 235418862-(3,5-Difluoro-2-nitro-phenyl)-malonic acid di-tert-butyl ester

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent2×

Procedure

To a suspension of NaH (54.6 g, 60%, 1.365 mol) in 600 mL of DMF was added di-t-Butyl malonate (118 g, 0.546 mol) at 0° C. and stirred for 30 min. 2,4,6 trifluoronitrobenzene was added as a solution in 400 mL of DMF (75 g, 0.42 mol) over 3 hours and the solution stirred at ambient temperature for 12 hours. The reaction mixture was extracted with ethyl acetate (3X's). The ethyl acetate was washed with water (3X's) and with brine and dried over MgSO4 and concentrated to give 62 g of crude product. LCMS [M+Na]-396; 1H NMR (500 MHz, DMSO) δ 7.81 (m, 1H), 7.27 (m, 1H), 5.00 (s, 1H), 1.41 (m, 18H).

Workup

  1. stirringthe solution stirred at ambient temperature for 12 hours
  2. extractionThe reaction mixture was extracted with ethyl acetate (3X's)
  3. washThe ethyl acetate was washed with water (3X's) and with brine
  4. dry with materialdried over MgSO4
  5. concentrationconcentrated

Sources & evidence

ORD record
ord-9b90622262e94ca6a8405c7bf99494ec
Source dataset
uspto-grants-2007_12
Patent number
US07312215B2

Reaction notes

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