Diiodomethane → Phenol, 4-(1-methylcyclopropyl)- (9CI)

HRID 2099146Notes

Reaction equation

HRID 2099146 reaction equation
[CH2:1]([Zn]CC)C.C([Si]([O:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]([CH3:22])=[CH2:21])=[CH:16][CH:15]=1)(C)C)(C)(C)C.ICI.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>ClC(Cl)C>[CH3:1][C:20]1([C:17]2[CH:16]=[CH:15][C:14]([OH:13])=[CH:19][CH:18]=2)[CH2:21][CH2:22]1

Participants

6

Reactant 4

HCID 6346DiiodomethaneHCID 2724141Tetrabutylammonium FluorideHCID 21898100HCID 21898100, compoundHCID 178418750HCID 178418750, compound

Product 1

HCID 17973047Phenol, 4-(1-methylcyclopropyl)- (9CI)Yield 68%

Reagents, catalysts & solvents 1

HCID 63651,1-DichloroethaneSolvent

Procedure

Diethylzinc (1.0 M in hexanes, 69 mL, 69 mmol) was added to a solution of tert-butyl-(4-isopropenyl-phenoxy)-dimethyl-silane (6.85 g, 27.6 mmol) in dichloroethane at 0° C. Diiodomethane (11.2 mL, 138 mmol) was then added dropwise to the solution and the resultant mixture was stirred at 0° C. for 0.5 h and allowed to warm to rt for 2 h. The opaque mixture was quenched with saturated aqueous NH4Cl. The aqueous phase was extracted with CH2Cl2 and the combined organic layers were washed with saturated aqueous NaHCO3. The organic layers were dried over sodium sulfate, filtered through celite, and concentrated. The crude TBS ether was dissolved in THF (50 mL) and TBAF (1.0 M in THF, 28 mL, 28 mmol) was added at rt. The solution was stirred for 2 h and then quenched with aqueous 1.0 M HCl. The aqueous phase was extracted with ethyl acetate and the combined organic layers were washed with saturated NaHCO3. The organic layers were dried over sodium sulfate, filtered and concentrated. Purification by silica-gel chromatography (1% 2-propanol/12% ethyl acetate in hexanes) provided 4-(1-methyl-cyclopropyl)-phenol (2.77 g, 68%) as a white solid.

Workup

  1. customThe opaque mixture was quenched with saturated aqueous NH4Cl
  2. extractionThe aqueous phase was extracted with CH2Cl2
  3. washthe combined organic layers were washed with saturated aqueous NaHCO3
  4. dry with materialThe organic layers were dried over sodium sulfate
  5. filtrationfiltered through celite
  6. concentrationconcentrated
  7. dissolutionThe crude TBS ether was dissolved in THF (50 mL)
  8. customquenched with aqueous 1.0 M HCl
  9. extractionThe aqueous phase was extracted with ethyl acetate
  10. washthe combined organic layers were washed with saturated NaHCO3
  11. dry with materialThe organic layers were dried over sodium sulfate
  12. filtrationfiltered
  13. concentrationconcentrated
  14. customPurification by silica-gel chromatography (1% 2-propanol/12% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-5c19c613203a404eabf271a87ab00192
Source dataset
uspto-grants-2009_08
Patent number
US07569568B2

Reaction notes

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