m-Chloroperbenzoic acid → HCID 70284007, compound

HRID 362268Notes

Reaction equation

HRID 362268 reaction equation
ClC1C=C(C=CC=1)C(OO)=[O:6].[CH3:12][O:13][C:14]1[CH:19]=[CH:18][C:17]([S:20][CH2:21][C:22]#[C:23][CH2:24][O:25][C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)=[CH:16][CH:15]=1>C(Cl)(Cl)Cl>[CH3:12][O:13][C:14]1[CH:15]=[CH:16][C:17]2[S:20][CH2:21][CH:22]([C:23](=[O:6])[CH2:24][O:25][C:26]3[CH:27]=[CH:28][CH:29]=[CH:30][CH:31]=3)[C:18]=2[CH:19]=1

Participants

4

Reactant 2

HCID 70297m-Chloroperbenzoic acidHCID 54051966HCID 54051966, compound

Product 1

HCID 70284007HCID 70284007, compound

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

A solution of m-chloroperoxybenzoic acid (55% purity; 15.2 g) in chloroform (300 ml) was added dropwise over 2.5 hours to a stirred, ice-cold solution of 1-(4-methoxyphenylthio)-4-phenoxybut-2-yne(13.7 g) in chloroform (125 ml), then the mixture was stirred at ambient temperature for 18 hours and filtered. The filtrate was washed with 5% sodium carbonate solution (3×150 ml) and water (3×100 ml), then dried (MgSO4) and filtered. The filtrate was heated under nitrogen at an external temperature of 80°-85° C. for 6 hours, allowed to stand at ambient temperature for 18 hours, heated at an external temperature of 80°-85° C. for a further 1.5 hours, then allowed to cool. The solvent was removed in vacuo, the residue was dissolved in dichloromethane (250 ml), and the solution was shaken vigorously for a few seconds with 5M aqueous sodium hydroxide solution (150 ml). The organic solution was separated, washed with water (2×150 ml), dried (MgSO4), and the solvent removed in vacuo. The residue was purified by flash chromatography over silica using 12.5-25% mixtures of ethyl acetate and petroleum ether (b.p. 60°-80° C.) as eluants. Appropriate fractions were combined, and the solvents removed in vacuo to leave 1-(5-methoxy-2,3-dihydrobenzo[b]thiophen-3-yl)-2-phenoxyethanone as a gum (4.5 g).

Workup

  1. filtrationfiltered
  2. washThe filtrate was washed with 5% sodium carbonate solution (3×150 ml) and water (3×100 ml)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. temperatureThe filtrate was heated under nitrogen at an external temperature of 80°-85° C. for 6 hours
  6. waitto stand at ambient temperature for 18 hours
  7. temperatureheated at an external temperature of 80°-85° C. for a further 1.5 hours
  8. temperatureto cool
  9. customThe solvent was removed in vacuo
  10. dissolutionthe residue was dissolved in dichloromethane (250 ml)
  11. stirringthe solution was shaken vigorously for a few seconds with 5M aqueous sodium hydroxide solution (150 ml)
  12. customThe organic solution was separated
  13. washwashed with water (2×150 ml)
  14. dry with materialdried (MgSO4)
  15. customthe solvent removed in vacuo
  16. customThe residue was purified by flash chromatography over silica using 12.5-25% mixtures of ethyl acetate and petroleum ether (b.p. 60°-80° C.) as eluants
  17. customthe solvents removed in vacuo

Sources & evidence

ORD record
ord-d5cfda5073f34c75b3c50876541239df
Source dataset
uspto-grants-1999_02
Patent number
US05869492

Reaction notes

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