1,3-Dibromopropane → HCID 18433146, compound

HRID 1452369Notes

Reaction equation

HRID 1452369 reaction equation
[H-].[Na+].[C:3]([O:6][C:7]1[C:12]([C:13]([CH3:16])([CH3:15])[CH3:14])=[CH:11][C:10]([OH:17])=[C:9]([CH3:18])[C:8]=1[C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:5])[CH3:4].Br[CH2:24][CH2:25][CH2:26]Br.[Cl-].[NH4+]>CN(C)C=O>[C:3]([O:6][C:7]1[C:12]([C:13]([CH3:14])([CH3:15])[CH3:16])=[CH:11][C:10]([O:17][CH2:26][CH:25]=[CH2:24])=[C:9]([CH3:18])[C:8]=1[C:19]([CH3:22])([CH3:21])[CH3:20])(=[O:5])[CH3:4]

Participants

6

Reactant 4

HCID 80011,3-DibromopropaneHCID 24758Sodium hydride2×HCID 25517Ammonium Chloride2×HCID 22918670HCID 22918670, compound2×

Product 1

HCID 18433146HCID 18433146, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

Sodium hydride (110 mg) was suspended in N,N-di-methylformamide (5 ml) and a solution of 4-acetoxy-3,5-di-tert-butyl-2-methylphenol (0.6 g) in N,N-dimethylformamide (5 ml) was added dropwise to the suspension at 0° C. After stirring for 30 min, 1,3-dibromopropane (0.36 ml) was added in one portion and the mixture was stirred for an additional 2 h. The reaction mixture was poured into a saturated aqueous solution of ammonium chloride and subjected to extraction with diethyl ether. The extract was washed with water and saturated brine, then dried over anhydrous sodium sulfate and the solvent was distilled off. The residue was dissolved in N,N-dimethylformamide (5 ml) and added to a solution prepared in the same manner as described above (4-acetoxy-3,5-di-tert-butyl-2-methylphenol, 0.4 g; sodium hydride, 86 mg; N,N-dimethylformamide, 5 ml). The mixture was allowed to warm from 0° C. to room temperature and stirred for 2 h. Subsequently, it was poured into a saturated aqueous solution of ammonium chloride and treated as described above. The residue was purified by silica gel chromatography (10% ethyl acetate in n-hexane). The first fraction gave 1-acetoxy-4-allyloxy-2,6-di-tert-butyl-3-methylbenzene (370 mg). The next fraction gave 1,3-bis(4-acetoxy-3,5-di-tert-butyl-2-methylphenoxy)propane (200 mg).

Workup

  1. stirringthe mixture was stirred for an additional 2 h
  2. extractionsubjected to extraction with diethyl ether
  3. washThe extract was washed with water and saturated brine
  4. dry with materialdried over anhydrous sodium sulfate
  5. distillationthe solvent was distilled off
  6. dissolutionThe residue was dissolved in N,N-dimethylformamide (5 ml)
  7. additionadded to a solution
  8. customprepared in the same manner
  9. temperatureto warm from 0° C. to room temperature
  10. stirringstirred for 2 h
  11. additiontreated
  12. customThe residue was purified by silica gel chromatography (10% ethyl acetate in n-hexane)

Sources & evidence

ORD record
ord-10e4ddbfb735499abd072ee84709d05e
Source dataset
uspto-grants-1997_02
Patent number
US05606089

Reaction notes

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