7-Chloro-2-methyl-1H-indene → 2-Methyl-7-phenylindene

HRID 1421452Notes

Reaction equation

HRID 1421452 reaction equation
Cl[C:2]1[CH:3]=[CH:4][CH:5]=[C:6]2[C:10]=1[CH2:9][C:8]([CH3:11])=[CH:7]2.[C:12]1([Mg]Br)[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1>CCOCC>[CH3:11][C:8]1[CH2:9][C:10]2[C:6]([CH:7]=1)=[CH:5][CH:4]=[CH:3][C:2]=2[C:12]1[CH:17]=[CH:16][CH:15]=[CH:14][CH:13]=1

Participants

4

Reactant 2

HCID 64227607-Chloro-2-methyl-1H-indeneHCID 178418255HCID 178418255, compound

Product 1

HCID 42924022-Methyl-7-phenylindene

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent2×

Conditions

Temperature
1 °C

Procedure

A 5L round bottom flask was equipped with mechanical stirring, a reflux condenser and ice bath. 488.2 g distilled 7-chloro-2-methylindene (2.97 mol) was added, dissolved in 2L ether and 32.2 g Ni(dpp) (0.059 mol, 2 mol %) slurried in the solution, and stirred to cool to 0-2° C. 1.05L of 3.1M phenylmagnesium bromide in ether (3.25 mol, 10% excess) was added slowly from an addition funnel so that the temperature remained below 5° C. Once complete, the ice bath was removed, and the reaction stirred up to room temperature. The reaction was refluxed for 8 hours, and checked for completion by GC. The reaction flask was cooled with an ice bath, and 250 mL water added, then 1L 10% HCl. The aqueous and organic layers are separated, and the organic layer dried over anhydrous Na2SO4. Ether was distilled, and the residual oil placed on a column of 100 g silica gel. Elution with hexane was performed, the hexane distilled under reduced pressure to a temperature of 90° C. 2-methyl-7-phenylindene (Spaleck compound 13a) was obtained by distillation at <1 mm Hg with a 36 cm Vigreux column at 125° C. A fore-cut containing biphenyl was obtained at 70-90° C. and discarded. Yield was 507.8 g (2.47 mol) equal to 80%.

Workup

  1. additionwas added
  2. customremained below 5° C
  3. customOnce complete, the ice bath was removed
  4. stirringthe reaction stirred up to room temperature
  5. temperatureThe reaction was refluxed for 8 hours
  6. temperatureThe reaction flask was cooled with an ice bath
  7. addition250 mL water added
  8. customThe aqueous and organic layers are separated
  9. dry with materialthe organic layer dried over anhydrous Na2SO4
  10. distillationEther was distilled
  11. washElution with hexane
  12. distillationthe hexane distilled under reduced pressure to a temperature of 90° C

Sources & evidence

ORD record
ord-94e2d1e3657f40158fdd8eb3bb3d6f8e
Source dataset
uspto-grants-2000_06
Patent number
US06075171

Reaction notes

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