Diethanolamine → 4-Chloro-3-(methylthio)phenol

HRID 724271Notes

Reaction equation

HRID 724271 reaction equation
B(Br)(Br)Br.[Cl:5][C:6]1[CH:11]=[CH:10][C:9]([O:12]C)=[CH:8][C:7]=1[S:14][CH3:15].N(CCO)CCO>ClCCl>[Cl:5][C:6]1[CH:11]=[CH:10][C:9]([OH:12])=[CH:8][C:7]=1[S:14][CH3:15]

Participants

5

Reactant 3

HCID 8113DiethanolamineHCID 25134Boron tribromideHCID 21877168(2-Chloro-5-methoxyphenyl)(methyl)sulfane

Product 1

HCID 218771864-Chloro-3-(methylthio)phenolYield 80.9%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Boron tribromide (1M in dichloromethane, 31 ml, 31 mmol) was added dropwise to a solution of 1-chloro-4-methoxy-2-(methylsulfanyl)benzene (2.88 g, 15 mmol) in dichloromethane (80 ml) at 0° C. The mixture was allowed to warm to room temperature, stirred for 72 h then cooled to 0° C. A solution of diethanolamine (10 ml) in dichloromethane (20 ml) was added dropwise (Caution—strong exotherm!) and the mixture was stirred at ambient temperature for 15 min once addition was complete, then partitioned between dichloromethane and 2N hydrochloric acid. The organic phase was washed with water, dried over MgSO4 and the solvent removed under reduced pressure. The residue was purified by flash column chromatography using ethyl acetate:cyclohexane (10:90 to 85:15) as eluant to give 4-chloro-3-(methylsulfanyl)phenol (2.12 g) as a brown oil.

Workup

  1. temperaturethen cooled to 0° C
  2. stirringthe mixture was stirred at ambient temperature for 15 min
  3. additiononce addition
  4. custompartitioned between dichloromethane and 2N hydrochloric acid
  5. washThe organic phase was washed with water
  6. dry with materialdried over MgSO4
  7. customthe solvent removed under reduced pressure
  8. customThe residue was purified by flash column chromatography

Sources & evidence

ORD record
ord-68141703564d462bab8d2aa263b9ebcb
Source dataset
uspto-grants-2006_11
Patent number
US07141586B2

Reaction notes

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