3-Chlorobenzoic Acid → 4-[4-(4-Fluorophenyl)-1,1-dimethylcyclopenta-2,4-dien-3-yl]benzenesulfonamide

HRID 36967

Reaction equation

HRID 36967 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][C:11]([CH3:14])([CH3:13])[CH2:10][C:9]=2[C:15]2[CH:20]=[CH:19][C:18]([S:21]([NH2:24])(=[O:23])=[O:22])=[CH:17][CH:16]=2)=[CH:4][CH:3]=1.ClC1C=C(C=CC=1)C(OO)=O.ClC1C=C(C=CC=1)C(O)=O.C([O-])(=O)C.[Na+]>ClCCl.C(O)(=O)C.O>[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[C:9]([C:15]3[CH:16]=[CH:17][C:18]([S:21]([NH2:24])(=[O:22])=[O:23])=[CH:19][CH:20]=3)=[CH:10][C:11]([CH3:14])([CH3:13])[CH:12]=2)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 4473-Chlorobenzoic AcidHCID 70297m-Chloroperbenzoic acidHCID 517045Sodium AcetateHCID 102690884-[2(4-Fluorophenyl)-4,4-dimethylcyclopenten-1-yl)benzenesulfonamide

Product 1

HCID 101545054-[4-(4-Fluorophenyl)-1,1-dimethylcyclopenta-2,4-dien-3-yl]benzenesulfonamideYield 67%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 1.0 g (2.89 mmol) of 4-[2-(4-fluorophenyl)-4,4-dimethylcyclopenten-1yl)benzenesulfonamide (from Step 2) in 20 mL of dichloromethane was treated with 800 mg (80% peroxyacid, 3.7 mmol) of m-chloroperoxybenzoic acid (MCPBA). The reaction was stirred at ambient temperature for 3 hours, washed with aqueous saturated sodium bisulfite, dried (MgSO4), and concentrated in vacuo to give a mixture of desired expoxide intermediate and m-chlorobenzoic acid; this crude mixture in 15 mL of acetic acid and 2 mL of water was subsequently treated with 1.0 g (12.2 mmol) of sodium acetate and stirred at 80° C. for 15 hours. The reaction mixture was cooled to ambient temperature and concentrated in vacuo. The residue was partitioned between water and ethyl acetate; the organic phase was washed with aqueous saturated sodiun bicarbonate, water, brine, dried (MgSO4), and reconcentrated in vacuo. Purification by silica gel chromatography gave 665 mg (67%) of 4-[4-(4-fluorophenyl)-1,1-dimethylcyclopenta-2,4-dien-3-yl]benzenesulfonamide as a colorless solid: mp 163.5°-164.5° C. (dec); NMR (CDCl3) d 1.33 (s, 6H), 4.83 (br s, 2H), 6.34 (d, J=2 Hz, 1H), 6.45 (d, J=2 Hz, 1H), 6.94 (t, J=9 Hz, 2H), 7.00-7.20 (m, 2H), 7.25 (d, J=8 Hz, 2H), 7.78 (d, J=8 Hz, 2H).

Workup

  1. washwashed with aqueous saturated sodium bisulfite
  2. dry with materialdried (MgSO4)
  3. concentrationconcentrated in vacuo
  4. customto give
  5. stirringstirred at 80° C. for 15 hours
  6. temperatureThe reaction mixture was cooled to ambient temperature
  7. concentrationconcentrated in vacuo
  8. customThe residue was partitioned between water and ethyl acetate
  9. washthe organic phase was washed with aqueous saturated sodiun bicarbonate, water, brine
  10. dry with materialdried (MgSO4)
  11. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-97954d74e57d4b73baee858bcd527947
Source dataset
uspto-grants-1995_05
Patent number
US05418254

Linked notes

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