HCID 57429409, compound → HCID 57429401, compound

HRID 2369776Notes

Reaction equation

HRID 2369776 reaction equation
[C:1]([CH:5]1[CH2:10][CH2:9][CH2:8][CH:7]([CH2:11][CH2:12][CH:13]2OCC[O:14]2)[CH2:6]1)([CH3:4])([CH3:3])[CH3:2]>O.O.O.O.O.O.[Fe](Cl)(Cl)Cl.ClCCl.CC(C)=O>[C:1]([CH:5]1[CH2:10][CH2:9][CH2:8][CH:7]([CH2:11][CH2:12][CH:13]=[O:14])[CH2:6]1)([CH3:4])([CH3:2])[CH3:3]

Participants

4

Reactant 1

HCID 57429409HCID 57429409, compound

Product 1

HCID 57429401HCID 57429401, compoundYield 41.2%

Reagents, catalysts & solvents 2

HCID 16211236Trichloroiron;hexahydrateCatalystHCID 21584124Propan-2-one--dichloromethane (1/1)Solvent

Procedure

2-[2-(3-tert-butylcyclohexyl)ethyl]-1,3-dioxolane (62 g, 0.22 mol, gc purity of 87%) and dichloromethane/acetone in a 4:1 ratio (3.7 L) were charged into a 5 L three-necked round-bottom flask equipped with a reflux condenser and a mechanical stirrer. Iron (III) chloride hexahydrate (212.3 g, 0.78 mol, 3.5 eq) was added to the reaction at ambient temperature. The reaction mixture was then stirred at ambient temperature for 4 h and subsequently quenched, at 5-10° C., with the addition of a saturated aqueous NaHCO3 (500 mL). The organic phase was then washed with brine (500 mL), dried over magnesium sulphate and concentrated. The resulting crude product was distilled via a Vigreux column (0.5 mBar, 82-85° C.), to give colourless oil (34.7 g, gc purity 79%). The oil was chromatographed on a silica gel column with 2% EtOAc in hexane as elution agent giving 3-(3-tert-butylcyclohexyl)propanal (17.8 g, gc purity>98%, ratio cis:trans 75:25; yield 40%).

Workup

  1. customequipped with a reflux condenser and a mechanical stirrer
  2. customsubsequently quenched, at 5-10° C., with the addition of a saturated aqueous NaHCO3 (500 mL)
  3. washThe organic phase was then washed with brine (500 mL)
  4. dry with materialdried over magnesium sulphate
  5. concentrationconcentrated
  6. distillationThe resulting crude product was distilled via a Vigreux column (0.5 mBar, 82-85° C.)
  7. customto give colourless oil (34.7 g, gc purity 79%)
  8. customThe oil was chromatographed on a silica gel column with 2% EtOAc in hexane as elution agent

Sources & evidence

ORD record
ord-32ca9d57a00d4a388e815601eabe94b0
Source dataset
uspto-grants-2014_04
Patent number
US08709994B2

Reaction notes

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