Monobenzone → Benzo(B)Thiophene

HRID 992

反応式

HRID 992 の反応式
Br[C:2]1[C:3]2[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=2[S:5][CH:6]=1.C(OC1C=CC(O)=CC=1)C1C=CC=CC=1>N1C(C)=CC(C)=CC=1C.C(OCC)(=O)C>[S:5]1[CH:6]=[CH:2][C:3]2[CH:10]=[CH:9][CH:8]=[CH:7][C:4]1=2

参加物

5

反応物 2

HCID 7638MonobenzoneHCID 123250Benzo(b)thiophene, 3-bromo-

生成物 1

HCID 7221Benzo(B)Thiophene収率 28%

試薬・触媒・溶媒 2

HCID 79532,4,6-Trimethylpyridine溶媒HCID 8857Ethyl Acetate溶媒

実験手順

To a solution of 3-bromo-benzo[b]thiophene (69.62 g, 0.325 mol) in 55 mL of anhydrous collidine under N2 was added 4-benzyloxyphenol (97.6 g, 0.488 mol) and cuprous oxide (23.3 g, 0.163 mol). The mixture was heated to reflux for 24 hours. Upon cooling, the reaction mixture was diluted with ethyl acetate (200 mL) and the crude mixture filtered through a pad of Celite® (Aldrich, Milwaukee, Wis.) to remove inorganic salts. The filtrate was washed with 1N hydrochloric acid (3×150 mL). The organic was dried (sodium sulfate) and concentrated in vacuo to a liquid. Thianaphthene was removed by distillation (10 mm Hg, 115°-120° C.). The remainder of the material was chromatographed (silicon dioxide, hexanes: ethyl acetate 85:15) to provide 12.2 g of benzo[b]thiophene and 12.95 g (35% based on recovered starting material) of [3-(4-benzyloxy)phenoxy]benzo-[b]thiophene as an off-white solid. mp 84°-86° C. 1H NMR (CDCl3) d 7.91-7.83 (m, 2H), 7.47-7.34 (m, 7H), 7.04 (q, JAB =9.0 Hz, 4H), 6.47 (s, 1H), 5.07 (s, 2H). Anal. Calcd. for C21H16O2S: C, 75.88; H, 4.85. Found: C, 75.75; H, 5.00.

後処理

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 24 hours
  3. temperatureUpon cooling
  4. filtrationthe crude mixture filtered through a pad of Celite® (Aldrich, Milwaukee, Wis.)
  5. customto remove inorganic salts
  6. washThe filtrate was washed with 1N hydrochloric acid (3×150 mL)
  7. dry with materialThe organic was dried (sodium sulfate)
  8. concentrationconcentrated in vacuo to a liquid
  9. customThianaphthene was removed by distillation (10 mm Hg, 115°-120° C.)
  10. customThe remainder of the material was chromatographed (silicon dioxide, hexanes: ethyl acetate 85:15)

出典と根拠

ORDレコード
ord-15ef5e371941461d87787ec3f8b02012
出典データセット
uspto-grants-1998_03
特許番号
US05723474

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