m-Chloroperbenzoic acid → 1-(4-Fluorophenyl)-2-(4-methylsulfonylphenyl)ethanone

HRID 1378583Notes

Reaction equation

HRID 1378583 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8](=[O:19])[CH:9]([C:11]2[CH:16]=[CH:15][C:14](SC)=[CH:13][CH:12]=2)Br)=[CH:4][CH:3]=1.[CH:20]1C=C(Cl)C=C(C(OO)=O)C=1.[OH:31][S:32]([O-:34])=O.[Na+]>C(Cl)Cl>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8](=[O:19])[CH2:9][C:11]2[CH:12]=[CH:13][C:14]([S:32]([CH3:20])(=[O:34])=[O:31])=[CH:15][CH:16]=2)=[CH:6][CH:7]=1

Participants

5

Reactant 3

HCID 70297m-Chloroperbenzoic acidHCID 23665763Sodium BisulfiteHCID 541605321-(4-Fluorophenyl)-2-(4-methylthiophenyl)-2-bromoethanone

Product 1

HCID 112433011-(4-Fluorophenyl)-2-(4-methylsulfonylphenyl)ethanoneYield 86%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a stirred solution of 1-(4-fluorophenyl)-2-(4-methylthiophenyl)ethanone (Example 1, Step 3) (15.00 g, 57.62 mmol) in methylene chloride (500 mL) at 5° C. (ice-bath) was added MCPBA (29.64 g, ca. 67% peroxide, ca. 113 mmol), portionwise over 30 minutes. The solution was warmed to room temperature. The reaction solution was stirred vigorously with NaHSO3 solution for 10 minutes to quench any unreacted MCPBA. The layers were separated and ethyl acetate was added to aid in dissolution of the precipitate which began to form. The partial suspension was filtered and the solid saved. The organic phase was washed successively with NaHCO3 solution and brine, dried over Na2SO4, and diluted with isooctane until a solid began to precipitate. Upon removal of most of the ethyl acetate and methylene chloride in vacuo more solid precipitated. All of the precipitates were combined yielding 1-(4-fluorophenyl)-2-(4-methylsulfonylphenyl)ethanone (14.5 g, 86%). mp 182°-183° C. 1H NMR (CDCl3) 300 mHz δ8.04 (dd, J=5.24, 8.46, 2H), 7.92 (d, J=8.26 Hz, 2H), 7.46 (d, J=8.46 Hz, 2H), 7.17 (t, J=8.46, 2H), 4.37 (s, 2H), 3.05 (s, 3H). MS: m/z 293 (MH+); HRMS A =1.6 mmu.

Workup

  1. customto quench any unreacted MCPBA
  2. customThe layers were separated
  3. additionethyl acetate was added to aid in dissolution of the precipitate which
  4. customto form
  5. filtrationThe partial suspension was filtered
  6. washThe organic phase was washed successively with NaHCO3 solution and brine
  7. dry with materialdried over Na2SO4
  8. additiondiluted with isooctane until a solid
  9. customto precipitate
  10. customUpon removal of most of the ethyl acetate and methylene chloride in vacuo more solid
  11. customprecipitated

Sources & evidence

ORD record
ord-c759c64de5dc4467b7db27815edacbfc
Source dataset
uspto-grants-1997_09
Patent number
US05668161

Reaction notes

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