Dichloromethane → 4-[(2-Bromo-6-methylphenanthridin-5(6H)-yl)sulfonyl]phenol

HRID 2181789Notes

Reaction equation

HRID 2181789 reaction equation
[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[N:12]([S:16]([C:19]3[CH:24]=[CH:23][C:22]([O:25]C)=[CH:21][CH:20]=3)(=[O:18])=[O:17])[CH:11]([CH3:27])[C:10]3[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=3)[C:4]=2[CH:3]=1.C1CCCCC=1.B(Br)(Br)Br.ClCCl>>[Br:1][C:2]1[CH:15]=[CH:14][C:13]2[N:12]([S:16]([C:19]3[CH:20]=[CH:21][C:22]([OH:25])=[CH:23][CH:24]=3)(=[O:18])=[O:17])[CH:11]([CH3:27])[C:10]3[C:5](=[CH:6][CH:7]=[CH:8][CH:9]=3)[C:4]=2[CH:3]=1

Participants

5

Reactant 4

HCID 6344DichloromethaneHCID 8079CyclohexeneHCID 25134Boron tribromideHCID 224823332-Bromo-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine

Product 1

HCID 104328134-[(2-Bromo-6-methylphenanthridin-5(6H)-yl)sulfonyl]phenolYield 68%

Procedure

A stirred suspension of 2-bromo-5-[(4-methoxyphenyl)sulfonyl]-6-methyl-5,6-dihydrophenanthridine (333 mg, 0.75 mmol) and cyclohexene (1.64 g, 20 mmol) was treated at room temperature under nitrogen with a solution of 1.0 M boron tribromide in dichloromethane (5 mL, 5 mmol). After stirring for approximately four hours at room temperature, the reaction was quenched with methanol (20 mL) and diluted with dichloromethane. The mixture was washed sequentially with an aqueous potassium carbonate solution, a saturated, aqueous sodium chloride solution, and water. The organic phase was dried over anhydrous sodium sulfate, filtered through a short column of silica gel, and eluted with ethyl acetate. The ethyl acetate phase was evaporated in vacuo to a crude orange residue (0.5 g). The crude residue was purified by preparative chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g) with gradient elution of between 10% to 30% methyl tert-butyl ether in hexane at a flow rate of 50 mL/min; and afforded, after evaporation of the solvent, a colorless oil. Crystallization of the colorless oil from a mixture of diethyl ether-hexane yielded the title compound (0.220 g, 0.51 mmol, 68%) as a homogeneous, off-white, crystalline solid, m.p. 201-203° C.;

Workup

  1. customthe reaction was quenched with methanol (20 mL)
  2. additiondiluted with dichloromethane
  3. washThe mixture was washed sequentially with an aqueous potassium carbonate solution
  4. dry with materialThe organic phase was dried over anhydrous sodium sulfate
  5. filtrationfiltered through a short column of silica gel
  6. washeluted with ethyl acetate
  7. customThe ethyl acetate phase was evaporated in vacuo to a crude orange residue (0.5 g)
  8. customThe crude residue was purified by preparative chromatography on a Biotage® 40 Mi column of pre-packed silica gel (90 g) with gradient elution of between 10% to 30% methyl tert-butyl ether in hexane at a flow rate of 50 mL/min
  9. customand afforded
  10. customafter evaporation of the solvent
  11. customCrystallization of the colorless oil
  12. additionfrom a mixture of diethyl ether-hexane

Sources & evidence

ORD record
ord-f6379c492d8d46d8a80a6218fe778eb4
Source dataset
uspto-grants-2005_05
Patent number
US06894061B2

Reaction notes

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