Potassium bisulfate → 1-[2-(4-Fluorophenyl)-4,4-dimethyl-1-cyclopentenyl]-4-methylsulfonylbenzene

HRID 2226008Notes

Reaction equation

HRID 2226008 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][C:5]([C:8]2[CH2:12][C:11]([CH3:14])([CH3:13])[CH2:10][C:9]=2[C:15]2[CH:20]=[CH:19][C:18](SC)=[CH:17][CH:16]=2)=[CH:4][CH:3]=1.O[O:24][S:25]([O-:27])=O.[K+].OS([O-])(=O)=O.[K+].[CH3:35]O.O>O>[F:1][C:2]1[CH:3]=[CH:4][C:5]([C:8]2[CH2:12][C:11]([CH3:14])([CH3:13])[CH2:10][C:9]=2[C:15]2[CH:16]=[CH:17][C:18]([S:25]([CH3:35])(=[O:27])=[O:24])=[CH:19][CH:20]=2)=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 516920Potassium bisulfateHCID 104482441-[2-(4-Fluorophenyl)-4,4-dimethylcyclopenten-1-yl]-4-(methylthio)benzeneHCID 22242641Methanol--water (1/1)HCID 23707502Potassium hydroxy sulfite

Product 1

HCID 98410791-[2-(4-Fluorophenyl)-4,4-dimethyl-1-cyclopentenyl]-4-methylsulfonylbenzeneYield 38%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

A solution of 120 mg (0.39 mmol) of 1-[2-(4-fluorophenyl)-4,4-dimethylcyclopenten-1-yl]-4-(methylthio)benzene (Step 9 ) in 3 mL of methanol/water (1:1) was slowly treated with 470 mg (0.76 mmol) of Oxone® [2 KHSO5.KHSO4.K2SO4 ] in 2 mL of water. After stirring for 4 h, the solvent was removed in vacuo. The residue was dissolved in ethyl acetate and washed with water and brine, dried (MgSO4), and reconcentrated. Purification by silica gel chromatography (MPLC) with hexane/ethyl acetate (5:1) and subsequent lyophilization from acetonitrile/water (1:1) gave 50 mg (38%) of 1-[2-(4-fluorophenyl)-4,4-dimethyl cyclopenten-1-yl]-4-(methylsulfonyl)benzene (41 in Synthetic Scheme X when R1 and R2 =CH3, R5 =F, R10 =SO2CH3, R3, R4, R6, R7, R8, R9, R11, and R12 =H) as a colorless solid: NMR (CDCl3) d 1.24 (s, 6H) , 2.71 (s, 4H), 3.4 (s, 3H), 6.92 (t, J=8 Hz, 2H), 7.05-7.12 (m, 2H) , 7.30 (d, J=9 Hz, 2H) , 7.75 (d, J=9 Hz, 3H); MS (EI) m/e (rel intensity) 344 (100) , 329 (33) , 250 (18) , 235 (20) , 109 (35) , 69 (44); HRMS. Calc'd for C20H21FO2S: 344.1246. Found: 344.1272.

Workup

  1. customthe solvent was removed in vacuo
  2. dissolutionThe residue was dissolved in ethyl acetate
  3. washwashed with water and brine
  4. dry with materialdried (MgSO4)
  5. customPurification by silica gel chromatography (MPLC) with hexane/ethyl acetate (5:1) and subsequent lyophilization from acetonitrile/water (1:1)

Sources & evidence

ORD record
ord-86f2f913179c4df8b6ad6cc462111eae
Source dataset
uspto-grants-1994_09
Patent number
US05344991

Reaction notes

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