Hydrochloric Acid → 4-Hydroxydibenzothiophene

HRID 1606767Notes

Reaction equation

HRID 1606767 reaction equation
[CH:1]1[C:9]2[C:8]3[CH:10]=[CH:11][CH:12]=[CH:13][C:7]=3[S:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.CN(C)CCN(C)C.C([Li])CCC.B(OCCCC)(OCCCC)[O:28]CCCC.OO.Cl>CCOCC>[OH:28][C:4]1[C:5]2[S:6][C:7]3[CH:13]=[CH:12][CH:11]=[CH:10][C:8]=3[C:9]=2[CH:1]=[CH:2][CH:3]=1

Participants

8

Reactant 6

HCID 313Hydrochloric AcidHCID 784Hydrogen PeroxideHCID 3023DibenzothiopheneHCID 8037N,N,N',N'-TetramethylethylenediamineHCID 12712Tributyl borateHCID 178418339Butyllithium

Product 1

HCID 1548734-HydroxydibenzothiopheneYield 57%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Procedure

Dibenzothiophene (18.4 g, 0.10 mole) and N,N,N',N'-tetramethylethylenediamine (14.0 g, 0.12 mole) were dissolved in 200 ml dry ether. Butyl lithium (0.1 mole) in ether was added dropwise under stirring at room temperature. The reaction mixture was then refluxed for 1 hour. The mixture was cooled to -70°C and freshly distilled tributyl borate (23.0 g, 0.10 mole) was added. After stirring for 2 hours the solution was allowed to warm up to room temperature. Perhydrol (19 ml) was added dropwise and the mixture was refluxed for 1.5 hours. Hydrochloric acid was added and the ether was separated. The ether was washed with 10 % ferrous ammonium sulphate solution and then extracted with sodium hydroxide solution. The alkaline aqueous solution was acidified and extracted with ether, which after evaporation gave 11.4 g (57 %) beige crystals. Recrystallization from aqueous methanol gave light-brownish needles with m.p. 167°-168°.

Workup

  1. temperatureThe reaction mixture was then refluxed for 1 hour
  2. temperatureThe mixture was cooled to -70°C
  3. stirringAfter stirring for 2 hours the solution
  4. temperatureto warm up to room temperature
  5. temperaturethe mixture was refluxed for 1.5 hours
  6. customthe ether was separated
  7. washThe ether was washed with 10 % ferrous ammonium sulphate solution
  8. extractionextracted with sodium hydroxide solution
  9. extractionextracted with ether, which
  10. customafter evaporation

Sources & evidence

ORD record
ord-aeee70ae34534c3ab16480b05e85c902
Source dataset
uspto-grants-1976_04
Patent number
US03953601

Reaction notes

Loading…