Ethanethiol → HCID 20484467, compound

HRID 648059Notes

Reaction equation

HRID 648059 reaction equation
[H-].[Na+].C(S)C.[H][H].C[O:9][C:10]1[C:11](OC)=[CH:12][C:13]2[S:19](=O)[CH2:18][CH2:17][CH2:16][CH2:15][C:14]=2[CH:21]=1>CN(C)C=O>[OH:9][C:10]1[CH:11]=[CH:12][C:13]2[S:19][CH:18]=[CH:17][CH:16]=[CH:15][C:14]=2[CH:21]=1

Participants

6

Reactant 4

HCID 6343Ethanethiol2×HCID 24758Sodium hydrideHCID 20484481HCID 20484481, compoundHCID 178418361HCID 178418361, compound

Product 1

HCID 20484467HCID 20484467, compound

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Sodium hydride (8.8 g of a 50% w/w dispersion in oil) was added over 30 minutes to a solution of ethanethiol (20.8 g) in dry dimethylformamide at 0°. After evolution of hydrogen had ceased additional ethanethiol (8.8 ml) was added followed by 7,8-dimethoxy-2,3,4,5-tetrahydro-1-benzothiepin-1-oxide. The mixture was heated at reflux for 3 hours, cooled and the solvent was removed in vacuo. The residue was taken up in water (100 ml) and extracted with diethyl ether (2×100 ml). The aqueous solution was acidified with conc. hydrochloric acid, saturated with solid sodium chloride and extracted with chloroform (2×100 ml). The organic extract was dried (Na2SO4) and the solvent was removed in vacuo to give a cream coloured solid. This material was chromatographed on a silica gel column eluting with methylene chloride/methanol mixtures (gradient 0 to 3% v/v methanol) to give the 7-hydroxybenzothiepin (20.7 g), m.p. 165°-166°. Further elution of the column gave, after recrystallisation from methanol, the isomeric 8-hydroxybenzothiepin (2.25 g), m.p. 173°-175°.

Workup

  1. additionwas added
  2. temperatureThe mixture was heated
  3. temperatureat reflux for 3 hours
  4. temperaturecooled
  5. customthe solvent was removed in vacuo
  6. extractionextracted with diethyl ether (2×100 ml)
  7. extractionextracted with chloroform (2×100 ml)
  8. extractionThe organic extract
  9. dry with materialwas dried (Na2SO4)
  10. customthe solvent was removed in vacuo
  11. customto give a cream
  12. customThis material was chromatographed on a silica gel column
  13. washeluting with methylene chloride/methanol mixtures (gradient 0 to 3% v/v methanol)

Sources & evidence

ORD record
ord-6e31a924aca64c3b966db5250dcf7a6f
Source dataset
uspto-grants-1983_10
Patent number
US04410548

Reaction notes

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