Monobenzone → HCID 15347456, compound

HRID 618461Notes

Reaction equation

HRID 618461 reaction equation
Br[C:2]1[C:3]2[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=2[S:5][CH:6]=1.[CH2:11]([O:18][C:19]1[CH:24]=[CH:23][C:22]([OH:25])=[CH:21][CH:20]=1)[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=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.[CH2:11]([O:18][C:19]1[CH:20]=[CH:21][C:22]([O:25][C:2]2[C:3]3[CH:10]=[CH:9][CH:8]=[CH:7][C:4]=3[S:5][CH:6]=2)=[CH:23][CH:24]=1)[C:12]1[CH:13]=[CH:14][CH:15]=[CH:16][CH:17]=1

Participants

6

Reactant 2

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

Product 2

HCID 7221Benzo(B)ThiopheneHCID 15347456HCID 15347456, compoundYield 35%

Reagents, catalysts & solvents 2

HCID 79532,4,6-TrimethylpyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

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 1 N hydrochloric acid (3×150 mL). The organic was dried with sodium sulfate and concentrated in vacuc 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-benzyloxyphenoxy)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).

Workup

  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 1 N hydrochloric acid (3×150 mL)
  7. dry with materialThe organic was dried with sodium sulfate
  8. concentrationconcentrated in vacuc 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)

Sources & evidence

ORD record
ord-0492fac1cfac47738a5d0e0ed5f429f4
Source dataset
uspto-grants-1999_09
Patent number
US05952513

Reaction notes

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