Ethyl Acetate → 1-(Bromomethyl)-4-(4-(trifluoromethoxy)benzyl)benzene

HRID 1496918Notes

Reaction equation

HRID 1496918 reaction equation
[F:1][C:2]([F:20])([F:19])[O:3][C:4]1[CH:18]=[CH:17][C:7]([CH2:8][C:9]2[CH:14]=[CH:13][C:12]([CH2:15]O)=[CH:11][CH:10]=2)=[CH:6][CH:5]=1.P(Br)(Br)[Br:22].CCOC(C)=O>C(Cl)Cl>[Br:22][CH2:15][C:12]1[CH:13]=[CH:14][C:9]([CH2:8][C:7]2[CH:17]=[CH:18][C:4]([O:3][C:2]([F:20])([F:19])[F:1])=[CH:5][CH:6]=2)=[CH:10][CH:11]=1

Participants

5

Reactant 3

HCID 8857Ethyl AcetateHCID 24614Phosphorus tribromideHCID 66707469(4-(4-(Trifluoromethoxy)benzyl)phenyl)methanol

Product 1

HCID 667073181-(Bromomethyl)-4-(4-(trifluoromethoxy)benzyl)benzeneYield 64%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

A solution of alcohol 95 (0.18 g, 0.64 mmol) in CH2Cl2 (4 mL) was treated with PBr3 (115 μL 1.2 mmol). The reaction mixture was stirred at room temperature for 2 h, then EtOAc (150 mL) was added. The organic layer was washed with water (100 mL), the aqueous layer was re-extracted with EtOAc (100 mL), and the combined organic layers were washed with brine (100 mL), dried (Na2SO4) and concentrated under reduced pressure. The residue was chromatographed on silica gel, eluting with petroleum ether/EtOAc (9:1), to give 1-(bromomethyl)-4-[4-(trifluoromethoxy)benzyl]benzene (96) (0.14 g, 64%) as a white solid: mp (EtOAc/hexane) 33-35° C.; 1H NMR (CDCl3) δ 7.34-7.30 (m, 2H), 7.20-7.10 (m, 6H), 4.48 (s, 2H), 3.97 (s, 2H); HREIMS calcd for C15H1279BrF3O m/z (M+) 344.0024, found 344.0033; calcd for C15H1281BrF3O m/z (M+) 346.0003, found 346.0011.

Workup

  1. washThe organic layer was washed with water (100 mL)
  2. extractionthe aqueous layer was re-extracted with EtOAc (100 mL)
  3. washthe combined organic layers were washed with brine (100 mL)
  4. dry with materialdried (Na2SO4)
  5. concentrationconcentrated under reduced pressure
  6. customThe residue was chromatographed on silica gel
  7. washeluting with petroleum ether/EtOAc (9:1)

Sources & evidence

ORD record
ord-59b017c9c2494fa2806294b3dbbd56c3
Source dataset
uspto-grants-2015_12
Patent number
US09198913B2

Reaction notes

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