Sodium hydride → Methyl alpha-[(2-Bromophenyl)methylene]-(2-carboxy-4-nitrophenyl)acetate

HRID 36636

Reaction equation

HRID 36636 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([C:15]([O:17]C)=[O:16])[C:7](=[CH:13][CH:14]=1)[CH2:8][C:9]([O:11][CH3:12])=[O:10])([O-:3])=[O:2].[H-].[Na+].[Br:21][C:22]1[CH:29]=[CH:28][CH:27]=[CH:26][C:23]=1[CH:24]=O>C1COCC1>[Br:21][C:22]1[CH:29]=[CH:28][CH:27]=[CH:26][C:23]=1[CH:24]=[C:8]([C:7]1[CH:13]=[CH:14][C:4]([N+:1]([O-:3])=[O:2])=[CH:5][C:6]=1[C:15]([OH:17])=[O:16])[C:9]([O:11][CH3:12])=[O:10]

Participants

5

Reactant 3

HCID 24758Sodium hydrideHCID 811292-BromobenzaldehydeHCID 123467632-Methoxycarbonylmethyl-5-nitro-benzoic acid methyl ester

Product 1

HCID 53738354Methyl alpha-[(2-Bromophenyl)methylene]-(2-carboxy-4-nitrophenyl)acetateYield 70.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

Dimethyl 4-nitrohomophthalate (Ghosh, C. K.; Mukherjee, K. K. J. Ind. Chem. Soc. 1976, 53, 662) (5 g, 0.02 tool) in THF (20 mL) was added to a suspension of sodium hydride (0.85 g of 60% disp., 0.021 mol) in THF (30 mL) with stirring at 0° C. under nitrogen. The resulting solution was stirred for 5-10 min and 2-bromobenzaldehyde (2.3 mL, 0.02 mol) was added in one portion. The cooling bath was removed after 10 min and the reaction was stirred at room temperature until the mixture solidified. The solid was dissolved in water and extracted with dichloromethane (2×). The aqueous phase was acidified and reextracted 3× with fresh portions of dichloromethane. The latter extracts were combined, washed with water and brine, dried over anhydrous magnesium sulfate, filtered, and evaporated. The residue crystallized on standing to give 5.62 g (70%) of off-white product: 1H NMR (300 MHz, CDCl3) δ 3.90 (3H, s), 6.66 (1H, d), 7.09 (1H, t), 7.16-7.23 (3H, m), 7.69 (1H, d), 7.86 (1H, s), 8.24 (1H, dd), 8.68 (1H, d); MS m/e 423-425 (M+NH4+).

Workup

  1. stirringThe resulting solution was stirred for 5-10 min
  2. customThe cooling bath was removed after 10 min
  3. stirringthe reaction was stirred at room temperature until the mixture
  4. dissolutionThe solid was dissolved in water
  5. extractionextracted with dichloromethane (2×)
  6. washwashed with water and brine
  7. dry with materialdried over anhydrous magnesium sulfate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue crystallized

Sources & evidence

ORD record
ord-f634b8b5c02d42ff9ba31e1bd4439e90
Source dataset
uspto-grants-1995_05
Patent number
US05416089

Linked notes

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