Triethylsilane → 4-Bromo-1-chloro-2-(4-ethoxy-benzyl)-benzene

HRID 2174325Notes

Reaction equation

HRID 2174325 reaction equation
[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:19])=[C:6]([C:8]([C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH3:18])=[CH:12][CH:11]=2)=O)[CH:7]=1.C([SiH](CC)CC)C.FC(F)(F)S(O)(=O)=O>FC(F)(F)C(O)=O>[Br:1][C:2]1[CH:3]=[CH:4][C:5]([Cl:19])=[C:6]([CH2:8][C:10]2[CH:15]=[CH:14][C:13]([O:16][CH2:17][CH3:18])=[CH:12][CH:11]=2)[CH:7]=1

Participants

5

Reactant 3

HCID 12052Triethylsilane2×HCID 62406Trifluoromethanesulfonic acidHCID 10020105(5-Bromo-2-chlorophenyl)(4-ethoxyphenyl)methanone

Product 1

HCID 99964494-Bromo-1-chloro-2-(4-ethoxy-benzyl)-benzeneYield 94.4%

Reagents, catalysts & solvents 1

HCID 6422Trifluoroacetic acidSolvent

Procedure

To (5-bromo-2-chlorophenyl)(4-ethoxyphenyl)methanone (1440 g, 4.26 mol) and triethylsilane (1.37 L, 8.6 mol) in trifluoroacetic acid (820 mL) was slowly added trifluoromethanesulfonic acid (1.9 mL). After refluxing for 6 hours, additional triethylsilane (400 mL, 2.47 mol) was added. After refluxing for another 8 hours, the mixture was evaporated under reduced pressure. The residue was dissolved in dichloromethane (20 L), washed with water (10 L), aqueous sodium carbonate (10 L), and brine (10 L), and concentrated to give crude product. The crude product was distilled to remove (Et3Si)2O under vacuum. The residue was recrystallized from absolute ethanol (5 L) and dried under vacuum to give compound 3 (1310 g, 94% yield, HPLC purity>99%).

Workup

  1. temperatureAfter refluxing for 6 hours
  2. temperatureAfter refluxing for another 8 hours
  3. customthe mixture was evaporated under reduced pressure
  4. dissolutionThe residue was dissolved in dichloromethane (20 L)
  5. washwashed with water (10 L), aqueous sodium carbonate (10 L), and brine (10 L)
  6. concentrationconcentrated
  7. customto give crude product
  8. distillationThe crude product was distilled
  9. customto remove (Et3Si)2O under vacuum
  10. customThe residue was recrystallized from absolute ethanol (5 L)
  11. customdried under vacuum

Sources & evidence

ORD record
ord-e231fa2d300b41a2b9f45406e73474d0
Source dataset
uspto-grants-2015_06
Patent number
US09061060B2

Reaction notes

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