3-Chlorobenzoic Acid → 4-[6-(4-Fluorophenyl)spiro[2.4]hepta-4,6-dien-5-yl]benzenesulfonamide

HRID 1379059Notes

Reaction equation

HRID 1379059 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:14][C:11]3([CH2:13][CH2:12]3)[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]3([CH:14]=2)[CH2:12][CH2:13]3)=[CH:4][CH:3]=1

Participants

8

Reactant 4

HCID 4473-Chlorobenzoic AcidHCID 70297m-Chloroperbenzoic acidHCID 517045Sodium AcetateHCID 99280474-[6-(4-Fluorophenyl)spiro[2.4]hept-5-en-5-yl]benzenesulfonamide

Product 1

HCID 99025674-[6-(4-Fluorophenyl)spiro[2.4]hepta-4,6-dien-5-yl]benzenesulfonamideYield 39.6%

Reagents, catalysts & solvents 3

HCID 176Acetic AcidSolventHCID 962WaterSolventHCID 6344DichloromethaneSolvent

Procedure

A solution of 300 mg (0.88. mmol) of 4-[6-(4-fluorophenyl)spiro[2.4]hept-5-en-5-yl]benzenesulfonamide (from Step 1) in 5 mL of dichloromethane was treated with 300 mg (55% peroxyacid, 0.96 mmol) of m-chloroperoxybenzoic acid (MCPBA). The reaction was stirred at ambient temperature for 2.5 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 6 mL of acetic acid and 0.6 mL of water was subsequently treated with 300 mg (3.7 mmol) of sodium acetate and stirred at 80° C. for 10 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 sodium bicarbonate, water, brine, dried (MgSO4), and reconcentrated in vacuo. Purification by silica gel chromatography gave 118 mg (39%) of 4-[6-(4-fluorophenyl)spiro[2.4]hepta-4,6-dien-5-yl]benzenesulfonamide as a colorless solid: mp 110°-116° C. (dec); NMR (CDCl3) δ 1.80 (s, 4H), 4.81 (br s, 2H), 6.21 (d, J=2 Hz, 1H), 6.33 (d, J=2 Hz, 1H), 6.94 (t, J=9 HZ, 2H), 7.06-7.15 (m, 2H), 7.29 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 10 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 sodium bicarbonate, water, brine
  10. dry with materialdried (MgSO4)
  11. customPurification by silica gel chromatography

Sources & evidence

ORD record
ord-b495e4b580de46f1b08d28d0267eb98a
Source dataset
uspto-grants-1997_09
Patent number
US05670510

Reaction notes

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