Dimethyl Sulfoxide → 2-bromo-8,9-dihydro-4H-cyclopenta[def]phenanthrene

HRID 2264117Notes

Reaction equation

HRID 2264117 reaction equation
[Br:1][C:2]1[CH:15]=[C:14]2[CH2:16][C:11]3[C:12]4=[C:13]2[C:4](=[CH:5][CH:6]=[C:7]4[CH:8]=[CH:9][CH:10]=3)[CH:3]=1.CC(O)(C)C.CS(C)=O.CI>C(Cl)Cl.O.CN(P(N(C)C)(N(C)C)=O)C>[Br:1][C:2]1[CH:15]=[C:14]2[CH2:16][C:11]3[C:12]4[C:13]2=[C:4]([CH2:5][CH2:6][C:7]=4[CH:8]=[CH:9][CH:10]=3)[CH:3]=1

Participants

8

Reactant 4

HCID 679Dimethyl SulfoxideHCID 6328Methyl iodideHCID 6386tert-ButanolHCID 125243622-bromo-4H-cyclopenta[def]phenanthrene

Product 1

HCID 125243632-bromo-8,9-dihydro-4H-cyclopenta[def]phenanthreneYield 172.4%

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 6344DichloromethaneSolventHCID 12679HexamethylphosphoramideSolvent

Procedure

2-bromo-4H-cyclopenta[def]phenanthrene (2.6 g, 7.7 mmol), t-BuOH (20.8 g, 61.6 mmol), DMSO (20 ml), and HMPA (20 ml) were put into a 50 ml round bottom flask using a syringe. The reaction mixture was stirred at room temperature for 50 minutes and cooled to 0° C. Then, CH3I (3.75 ml, 61.6 mmol) was dropwise added to the flask using a syringe at 0° C. and the reaction mixture was stirred at 0° C. for 30 minutes. Then, water (50 ml) and methylene chloride (50 ml) were added to the flask to separate an organic phase. The organic phase was purified by silica gel column chromatography to give a compound 2 (3.6 g, 80%). 1H NMR (300 MHz, CDCl3, δ): 7.98 (2H, s), 7.79 (2H, s), 7.73 (2H, s), 6.94 (dd, 1H), 1.93 (m, 6H).

Workup

  1. temperaturecooled to 0° C
  2. customat 0° C.
  3. stirringthe reaction mixture was stirred at 0° C. for 30 minutes
  4. customto separate an organic phase
  5. customThe organic phase was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-29b9df69b9e540b4aaa86ede0d68af5d
Source dataset
uspto-grants-2010_12
Patent number
US07854999B2

Reaction notes

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