1,3,5-Tribromobenzene → HCID 50994271, compound

HRID 1784858Notes

Reaction equation

HRID 1784858 reaction equation
Br[C:2]1[CH:7]=[C:6]([Br:8])[CH:5]=[C:4]([Br:9])[CH:3]=1.[Li]CCCC.[Cl:15][C:16]1[CH:17]=[C:18]([CH:25]=[C:26]([CH3:28])[N:27]=1)[C:19](N(OC)C)=[O:20].C(=O)(O)[O-].[Na+]>CCOCC.C1COCC1.C(OCC)(=O)C>[Cl:15][C:16]1[CH:17]=[C:18]([C:19]([C:2]2[CH:7]=[C:6]([Br:8])[CH:5]=[C:4]([Br:9])[CH:3]=2)=[O:20])[CH:25]=[C:26]([CH3:28])[N:27]=1

Participants

8

Reactant 4

HCID 122791,3,5-TribromobenzeneHCID 516892Sodium BicarbonateHCID 50994266HCID 50994266, compoundHCID 178418339Butyllithium

Product 1

HCID 50994271HCID 50994271, compoundYield 77%

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-78 °C

Procedure

To 0.45 grams (1.4 mmol) of 1,3,5-tribromobenzene in 25.0 mL of anhydrous ether at −78° C. was added 0.57 mL of 2.5 M n-BuLi (1.4 mmol) at a rate that maintained the internal temperature of the reaction at less than −70° C. After the addition was complete, the reaction was stirred 1 hour at −78° C., then 0.220 grams (1.1 mmol) of 2-chloro-N-methoxy-6,N-dimethyl-isonicotinamide in 2 mL of THF was added, again keeping the temperature below −70° C. After the addition was complete, the reaction was allowed to stir at −25° C. for 45 minutes; then 100 mL saturated aqueous sodium bicarbonate was added and the reaction was stirred at room temperature for 30 minutes. The phases were separated and the aqueous phase was extracted with ether. The organic fractions were combined and dried with sodium sulfate. The volatiles were removed under reduced pressure and the crude product was chromatographed on silica gel using 5:1 hexane:ethyl acetate to give 330 mg (77% yield) of (2-chloro-6-methyl-pyridin-4-yl)-(3,5-dibromo-phenyl)-methanone.

Workup

  1. temperaturemaintained
  2. customthe internal temperature of the reaction at less than −70° C
  3. additionAfter the addition
  4. customthe temperature below −70° C
  5. additionAfter the addition
  6. stirringto stir at −25° C. for 45 minutes
  7. stirringthe reaction was stirred at room temperature for 30 minutes
  8. customThe phases were separated
  9. extractionthe aqueous phase was extracted with ether
  10. dry with materialdried with sodium sulfate
  11. customThe volatiles were removed under reduced pressure
  12. customthe crude product was chromatographed on silica gel using 5:1 hexane

Sources & evidence

ORD record
ord-ccb9c1d832214addb7fa98780978663c
Source dataset
uspto-grants-2009_03
Patent number
US07504401B2

Reaction notes

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