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

HRID 481826Notes

Reaction equation

HRID 481826 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×

Procedure

A 5 L 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 2 L ether and 32.2 g Ni(dpp) (0.059 mol, 2 mol %) slurried in the solution, and stirred to cool to 0°-2° C. 1.05 L 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 1 L 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. customA 5 L round bottom flask was equipped with mechanical stirring, a reflux condenser and ice bath
  2. additionwas added
  3. temperatureto cool to 0°-2° C
  4. customremained below 5° C
  5. customOnce complete, the ice bath was removed
  6. stirringthe reaction stirred up to room temperature
  7. temperatureThe reaction was refluxed for 8 hours
  8. temperatureThe reaction flask was cooled with an ice bath
  9. addition250 mL water added
  10. customThe aqueous and organic layers are separated
  11. dry with materialthe organic layer dried over anhydrous Na2SO4
  12. distillationEther was distilled
  13. washElution with hexane
  14. distillationthe hexane distilled under reduced pressure to a temperature of 90° C

Sources & evidence

ORD record
ord-2cc975949ee44bd1b4de887be4f7dc12
Source dataset
uspto-grants-1998_08
Patent number
US05789634

Reaction notes

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