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

HRID 1379723ノート

反応式

HRID 1379723 の反応式
[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.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

参加物

7

反応物 4

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

生成物 1

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

試薬・触媒・溶媒 2

HCID 962Water溶媒HCID 6344Dichloromethane溶媒

実験手順

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 acenic 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),

後処理

  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

出典と根拠

ORDレコード
ord-7236c1e94ce941ea9020e2e24052af47
出典データセット
uspto-grants-1997_09
特許番号
US05672627

反応ノート

読み込み中…