Dimethyl Sulfoxide → 2-Bromo-4-(3,5-di-tert-butylphenyl)-1H-indene

HRID 923729Notes

Reaction equation

HRID 923729 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([C:15]2[CH:23]=[CH:22][CH:21]=[C:20]3[C:16]=2[CH:17]=[CH:18][CH2:19]3)[CH:8]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].CS(C)=O.[Br:28]N1C(=O)CCC1=O.C1(C)C=CC(S(O)(=O)=O)=CC=1>O>[Br:28][C:18]1[CH2:19][C:20]2[C:16]([CH:17]=1)=[C:15]([C:7]1[CH:8]=[C:9]([C:11]([CH3:14])([CH3:13])[CH3:12])[CH:10]=[C:5]([C:1]([CH3:2])([CH3:3])[CH3:4])[CH:6]=1)[CH:23]=[CH:22][CH:21]=2

Participants

6

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6101p-Toluenesulfonic acidHCID 67184N-bromobutanimideHCID 220230394-(3,5-Di-t-butylphenyl)indene

Product 1

HCID 1178183262-Bromo-4-(3,5-di-tert-butylphenyl)-1H-indeneYield 66.4%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A cold solution (5° C.) of compound 5 (49 g, 161 mmol, 1 equiv), dimethyl sulfoxide (500 mL) and water (5 mL) was treated in one portion with N-bromosuccinimide (43 g, 241 mmol, 1.5 equiv). The bath was removed and the reaction allowed to stir at room temperature overnight. The reaction was poured into water (1 L) and the mixture extracted with ethyl acetate (2×500 mL). The combined organic layers were washed with saturated brine (1 L), dried over sodium sulfate and concentrated under reduced pressure. The resulting residue was dissolved in toluene (500 mL) and p-toluenesulfonic acid (6.2 g, 32.6 mmol, 0.2 equiv) was added. The mixture was refluxed for 20 hours while removing water with a Dean-Stark trap. The reaction was cooled to room temperature and concentrated under reduced pressure. The resulting residue was purified over silica gel (1 Kg) eluting with heptanes to give compound 6 (41 g, 66% yield) as a white solid.

Workup

  1. customThe bath was removed
  2. additionThe reaction was poured into water (1 L)
  3. extractionthe mixture extracted with ethyl acetate (2×500 mL)
  4. washThe combined organic layers were washed with saturated brine (1 L)
  5. dry with materialdried over sodium sulfate
  6. concentrationconcentrated under reduced pressure
  7. dissolutionThe resulting residue was dissolved in toluene (500 mL)
  8. temperatureThe mixture was refluxed for 20 hours
  9. customwhile removing water with a Dean-Stark trap
  10. temperatureThe reaction was cooled to room temperature
  11. concentrationconcentrated under reduced pressure
  12. customThe resulting residue was purified over silica gel (1 Kg)
  13. washeluting with heptanes

Sources & evidence

ORD record
ord-b712024c6f774771a8cd6b4ca86e13c0
Source dataset
uspto-grants-2016_03
Patent number
US09279024B2

Reaction notes

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