Methanol → Racemic methyl-3-azido-2-hydroxy-1-methyl-cyclohexane-carboxylate

HRID 527063Notes

Reaction equation

HRID 527063 reaction equation
[CH3:1][O:2][C:3]([C:5]1([CH3:12])[C@@H:11]2[C@@H:9]([O:10]2)[CH2:8][CH2:7][CH2:6]1)=[O:4].CO.[NH4+].[Cl-].[N-:17]=[N+:18]=[N-:19].[Na+]>O>[CH3:1][O:2][C:3]([C:5]1([CH3:12])[CH2:6][CH2:7][CH2:8][CH:9]([N:17]=[N+:18]=[N-:19])[CH:11]1[OH:10])=[O:4]

Participants

6

Reactant 4

HCID 887MethanolHCID 25517Ammonium ChlorideHCID 33557Sodium AzideHCID 87339583Racemic cis-methyl 5-methyl-7-oxabicyclo[4.1.0]heptane-5-carboxylate2×

Product 1

HCID 90693494Racemic methyl-3-azido-2-hydroxy-1-methyl-cyclohexane-carboxylate

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

Racemic cis-methyl-5-methyl-7-oxabicyclo[4.1.0]heptane-5-carboxylate, 66b, (2.2 g, 12.93 mmol) was added to a flask containing MeOH (90 mL) and H2O (10 mL) under nitrogen atmosphere. NH4Cl (1.38 g, 0.90 mL, 25.86 mmol) and NaN3 (2.52 g, 38.79 mmol) were then added to the reaction mixture. The mixture was heated to reflux for 16 hours. The solvent was evaporated under reduced pressure and the oil was taken up in H2O and extracted with EtOAc. The combined organic phases were washed with brine and dried over Na2SO4. The crude product was purified by silica gel chromatography to afford 900 mg of racemic methyl-3-azido-2-hydroxy-1-methyl-cyclohexanecarboxylate.

Workup

  1. temperatureThe mixture was heated
  2. temperatureto reflux for 16 hours
  3. customThe solvent was evaporated under reduced pressure
  4. extractionextracted with EtOAc
  5. washThe combined organic phases were washed with brine
  6. dry with materialdried over Na2SO4
  7. customThe crude product was purified by silica gel chromatography

Sources & evidence

ORD record
ord-6141f6349e6945689434adb0d76fe93a
Source dataset
uspto-grants-2016_05
Patent number
US09345708B2

Reaction notes

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