1-Bromo-2-methylpropane → HCID 23023861, compound

HRID 851864Notes

Reaction equation

HRID 851864 reaction equation
[CH2:1](Br)[CH:2]([CH3:4])[CH3:3].[C:6]([C:8]1[CH:9]=[C:10]([CH:16]=[CH:17][C:18]=1O)[C:11]([O:13][CH2:14][CH3:15])=[O:12])#[N:7].C(=O)([O-])[O-].[K+].[K+]>CN(C=O)C>[C:6]([C:8]1[CH:9]=[C:10]([CH:16]=[CH:17][C:18]=1[CH2:1][CH:2]([CH3:4])[CH3:3])[C:11]([O:13][CH2:14][CH3:15])=[O:12])#[N:7]

Participants

5

Reactant 3

HCID 65551-Bromo-2-methylpropaneHCID 11430Potassium CarbonateHCID 21322395Ethyl 3-cyano-4-hydroxybenzoate

Product 1

HCID 23023861HCID 23023861, compoundYield 33%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Conditions

Temperature
100 °C

Procedure

Isobutyl bromide (56.1 mL, 512 mmol) was added to a suspension of the ethyl 3-cyano-4-hydroxybenzoate crude product (51.4 g) and potassium carbonate (70.8 g, 512 mmol) in dry DMF (200 mL), stirred at 100° C. for 10 hours, and cooled to room temperature. Ice-water (500 mL) was then added to the cooled suspension. The aqueous mixture was extracted with ethyl acetate (200 mL×2). The ethyl acetate portion was washed successively with water (500 mL×2) and aqueous saturated brine (200 mL), dried over anhydrous sodium sulfate, and placed under reduced pressure to distill the solvent off. The residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/4). The resulting crystalline product was dissolved in ethyl acetate (50 mL) under heating. The mixture was kept hot, while hexane (100 mL) was added to the mixture. The hexane solution was stirred and cooled to room temperature, and further stirred for 10 min. under cooling with ice. The precipitated crystalline product was collected by filtration, washed successively with ethyl acetate/hexane (1/5, 60 mL) mixture and hexane (500 mL), and dried in air, to give 20.8 g (yield 33%) of the desired compound in the form of a pale yellow crystalline product.

Workup

  1. temperaturecooled to room temperature
  2. extractionThe aqueous mixture was extracted with ethyl acetate (200 mL×2)
  3. washThe ethyl acetate portion was washed successively with water (500 mL×2) and aqueous saturated brine (200 mL)
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationto distill the solvent off
  6. customThe residue was purified by silica gel column chromatography (ethyl acetate/hexane=1/4)
  7. dissolutionThe resulting crystalline product was dissolved in ethyl acetate (50 mL)
  8. temperatureunder heating
  9. additionwas added to the mixture
  10. stirringThe hexane solution was stirred
  11. temperaturecooled to room temperature
  12. stirringfurther stirred for 10 min.
  13. temperatureunder cooling with ice
  14. filtrationThe precipitated crystalline product was collected by filtration
  15. washwashed successively with ethyl acetate/hexane (1/5, 60 mL) mixture and hexane (500 mL)
  16. customdried in air

Sources & evidence

ORD record
ord-32f8e2c1ac774e95a93b3bd1b8acc098
Source dataset
uspto-grants-2007_08
Patent number
US07253154B2

Reaction notes

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