Water → (2-Bromophenyl)(p-tolyl)sulfane

HRID 1811352Notes

Reaction equation

HRID 1811352 reaction equation
CC(C)([O-])C.[K+].[CH3:7][C:8]1[CH:13]=[CH:12][C:11]([SH:14])=[CH:10][CH:9]=1.[Br:15][C:16]1[CH:21]=[CH:20][CH:19]=[CH:18][C:17]=1Br.O>CN1CCCC1=O.C1(C)C=CC=CC=1>[C:8]1([CH3:7])[CH:13]=[CH:12][C:11]([S:14][C:17]2[CH:18]=[CH:19][CH:20]=[CH:21][C:16]=2[Br:15])=[CH:10][CH:9]=1

Participants

7

Reactant 4

HCID 962WaterHCID 78114-MethylbenzenethiolHCID 114141,2-DibromobenzeneHCID 23665647Potassium tert-butoxide

Product 1

HCID 21864904(2-Bromophenyl)(p-tolyl)sulfane

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 13387N-methyl-2-pyrrolidoneSolvent2×

Conditions

Temperature
100 °C

Procedure

To a stirred solution of potassium tert-butoxide (75 g, 0.668 mol, 1.1 eq) in N-methyl-2-pyrrolidone (225 mL) a solution of 4-methylthiophenol (78 g, 0.628 mol, 1.0 eq) dissolved in N-methyl-2-pyrrolidone (225 mL) was added. To the reaction mixture was then added to 1,2-dibromobenzene (73 mL, 605 mol, 1.0 eq); once the addition was complete the reaction mixture was warmed to 100° C. and maintained at this temperature for approximately 22 hrs. (The reaction is monitored by HPLC). After cooling to room temperature water (750 mL) and toluene (375 mL) were added, the phases separated, and the water phase extracted with toluene (250 mL). The organic phases were combined and the organic phase was concentrated by vacuum distillation. Once the distillation was complete, the residue was cooled and methanol (750 mL) added. The solvents were removed from the organic phase by vacuum distillation and further methanol (250 mL) added. Stirring over night at room temperature precipitated 2-(4-tolylsulfanyl)-phenyl bromide which was isolated by filtration, washed with methanol (260 mL) and dried in vacuum. Yield=120.8 g.

Workup

  1. additionwas added
  2. additiononce the addition
  3. temperaturemaintained at this temperature for approximately 22 hrs
  4. additionwere added
  5. customthe phases separated
  6. extractionthe water phase extracted with toluene (250 mL)
  7. concentrationthe organic phase was concentrated by vacuum distillation
  8. distillationOnce the distillation
  9. temperaturethe residue was cooled
  10. additionmethanol (750 mL) added
  11. customThe solvents were removed from the organic phase by vacuum distillation and further methanol (250 mL)
  12. additionadded
  13. customprecipitated 2-(4-tolylsulfanyl)-phenyl bromide which
  14. customwas isolated by filtration
  15. washwashed with methanol (260 mL)
  16. customdried in vacuum

Sources & evidence

ORD record
ord-2813429c527740aab9aab3fbb1711be3
Source dataset
uspto-grants-2013_01
Patent number
US08362255B2

Reaction notes

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