Benzyl Bromide → 1-(2,4-Bis-benzyloxy-3-iodo-phenyl)-2-methyl-propan-1-one

HRID 2355264Notes

Reaction equation

HRID 2355264 reaction equation
[OH:1][C:2]1[C:7]([I:8])=[C:6]([OH:9])[CH:5]=[CH:4][C:3]=1[C:10](=[O:14])[CH:11]([CH3:13])[CH3:12].[CH2:15](Br)[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1.C(=O)([O-])[O-].[Cs+].[Cs+]>CN(C)C=O>[CH2:15]([O:1][C:2]1[C:7]([I:8])=[C:6]([O:9][CH2:10][C:3]2[CH:4]=[CH:5][CH:6]=[CH:7][CH:2]=2)[CH:5]=[CH:4][C:3]=1[C:10](=[O:14])[CH:11]([CH3:12])[CH3:13])[C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][CH:17]=1

Participants

5

Reactant 3

HCID 7498Benzyl BromideHCID 10796Cesium carbonateHCID 671755911-(2,4-Dihydroxy-3-iodo-phenyl)-2-methyl-propan-1-one

Product 1

HCID 671763131-(2,4-Bis-benzyloxy-3-iodo-phenyl)-2-methyl-propan-1-oneYield 158.7%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Combine 1-(2,4-dihydroxy-3-iodo-phenyl)-2-methyl-propan-1-one (1357 g, 4.43 mol), benzyl bromide (1345 mL, 11.28 mol), and cesium carbonate (2460 g, 7.55 mol) in dimethylformamide (12 L) in a 22-L Morton flask and stir at room temperature overnight. Filter the salts and concentrate the filtrate (8 L of dimethylformamide is evaporated off). Combine residue with the salts, dilute with water (10 L) and extract with 2:1 ethyl acetate/toluene (2×6 L). Wash extracts with water (3×4 L), brine, dry with magnesium sulfate, filter, and evaporate. Stir the resulting solid in 9 L of 10% ethyl acetate in hexane for 1 hr, filter, wash solid with hexanes and air dry to provide the title compound (1710 g, 79% yield) as an off-white solid. HPLC Rt=6.60 min; 1H NMR (DMSO-d6) δ 7.61 (d, J=8.0 Hz, 1H), 7.4 (m, 10H), 6.99 (d, J=8.0 Hz, 1H), 5.27 (s, 2H), 4.84 (s, 2H), 3.43 (hept, J=8.0 Hz, 1H), 0.99 (d, J=8.0 Hz, 6H).

Workup

  1. filtrationFilter the salts
  2. concentrationconcentrate
  3. customthe filtrate (8 L of dimethylformamide is evaporated off)
  4. additionCombine residue with the salts, dilute with water (10 L)
  5. extractionextract with 2:1 ethyl acetate/toluene (2×6 L)
  6. washWash
  7. dry with materialdry with magnesium sulfate
  8. filtrationfilter
  9. customevaporate
  10. filtrationfilter
  11. washwash solid with hexanes and air
  12. customdry

Sources & evidence

ORD record
ord-9a20152d77844b9b923794770ab8ee2b
Source dataset
uspto-grants-2010_07
Patent number
US07754742B2

Reaction notes

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