Hydrochloric Acid → Tert-butyl 2-(4-bromo-2-nitrobenzoyl)-3-oxobutanoate

HRID 69111

Reaction equation

HRID 69111 reaction equation
[Cl-].[Mg+2].[Cl-].[O:4]=[C:5]([CH3:14])[CH2:6][C:7]([O:9][C:10]([CH3:13])([CH3:12])[CH3:11])=[O:8].[Br:15][C:16]1[CH:24]=[CH:23][C:19]([C:20](Cl)=[O:21])=[C:18]([N+:25]([O-:27])=[O:26])[CH:17]=1.Cl>O1CCCC1.C(OCC)(=O)C.O.N1C=CC=CC=1>[Br:15][C:16]1[CH:24]=[CH:23][C:19]([C:20]([CH:6]([C:5](=[O:4])[CH3:14])[C:7]([O:9][C:10]([CH3:11])([CH3:13])[CH3:12])=[O:8])=[O:21])=[C:18]([N+:25]([O-:27])=[O:26])[CH:17]=1

Participants

9

Reactant 4

HCID 313Hydrochloric AcidHCID 15538Tert-butyl acetoacetateHCID 5360315Magnesium ChlorideHCID 189198804-Bromo-2-nitrobenzoyl chloride

Product 1

HCID 86694315Tert-butyl 2-(4-bromo-2-nitrobenzoyl)-3-oxobutanoateYield 64%

Reagents, catalysts & solvents 4

HCID 962WaterSolventHCID 1049PyridineSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-8 °C

Procedure

Under a nitrogen atmosphere, to a suspension of 2.28 g of magnesium chloride in 50 mL of tetrahydrofuran was added 3.80 g of tert-butyl 3-oxobutanoate at room temperature. The mixture was cooled to −8° C., and 3.9 mL of pyridine was added thereto, followed by stirring at the same temperature for 30 minutes, warming to room temperature, and further stirring for 30 minutes. The mixture was cooled to −8° C., and a solution of 5.3 g of 4-bromo-2-nitrobenzoyl chloride in 20 mL of tetrahydrofuran was added thereto, followed by stirring at the same temperature for 1 hour, warming to room temperature, and further stirring for 1.5 hours. The mixture was poured into a mixture of water and ethyl acetate, and adjusted to pH 3 with concentrated hydrochloric acid. The aqueous layer was separated, and then the organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine, and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure to obtain 4.95 g of tert-butyl 2-(4-bromo-2-nitrobenzoyl)-3 -oxobutanoate.

Workup

  1. temperaturewarming to room temperature
  2. stirringfurther stirring for 30 minutes
  3. temperatureThe mixture was cooled to −8° C.
  4. stirringby stirring at the same temperature for 1 hour
  5. temperaturewarming to room temperature
  6. stirringfurther stirring for 1.5 hours
  7. customThe aqueous layer was separated
  8. washthe organic layer was washed with a saturated aqueous sodium hydrogen carbonate solution and saturated brine
  9. dry with materialdried over anhydrous magnesium sulfate
  10. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-2785f0f145504683ba851c929693a5f8
Source dataset
uspto-grants-2014_09
Patent number
US08822448B2

Linked notes

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