Cerium(III) chloride → Methyl 4-(4-hydroxy-4-methylcyclohex-1-en-1-yl)benzoate

HRID 2085791Notes

Reaction equation

HRID 2085791 reaction equation
[Cl-].[Ce+3].[Cl-].[Cl-].[CH3:5][Li].[Cl-].[Li+].[O:9]=[C:10]1[CH2:15][CH2:14][C:13]([C:16]2[CH:25]=[CH:24][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:18][CH:17]=2)=[CH:12][CH2:11]1>C1COCC1.C(OCC)C.C(OCC)(=O)C>[OH:9][C:10]1([CH3:5])[CH2:15][CH2:14][C:13]([C:16]2[CH:17]=[CH:18][C:19]([C:20]([O:22][CH3:23])=[O:21])=[CH:24][CH:25]=2)=[CH:12][CH2:11]1

Participants

8

Reactant 4

HCID 24636Cerium(III) chlorideHCID 433294Lithium ChlorideHCID 22730167Methyl 4-(4-oxocyclohex-1-en-1-yl)benzoateHCID 178418348HCID 178418348, compound

Product 1

HCID 22730725Methyl 4-(4-hydroxy-4-methylcyclohex-1-en-1-yl)benzoate

Reagents, catalysts & solvents 3

HCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A suspension of anhydrous cerium(III) chloride (2.71 g, 11 mmol) in THF (10 mL) at −78° C. was slowly treated with 1.5M methyllithium complexed with lithium chloride in diethyl ether (6.7 mL), warmed to room temperature over 2 hours, and added to a solution of Example 420C (1.15 g, 5.0 mmol) in THF (10 mL) at −78° C. The reaction was gradually warmed to room temperature over 4 hours, diluted with ethyl acetate (100 mL), washed with water (45 mL) and brine (10 mL), dried (MgSO4), filtered, and concentrated. The concentrate was purified by flash column chromatography on silica gel with 10-30% ethyl acetate/hexanes to provide the desired product.

Workup

  1. temperatureThe reaction was gradually warmed to room temperature over 4 hours
  2. washwashed with water (45 mL) and brine (10 mL)
  3. dry with materialdried (MgSO4)
  4. filtrationfiltered
  5. concentrationconcentrated
  6. customThe concentrate was purified by flash column chromatography on silica gel with 10-30% ethyl acetate/hexanes

Sources & evidence

ORD record
ord-7cb432e91c93475492c54c9ee4219287
Source dataset
uspto-grants-2004_04
Patent number
US06720338B2

Reaction notes

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