Nitric Acid → (1R,6S)-2,2,6-Trimethylcyclohexanecarboxylic acid

HRID 1975641Notes

Reaction equation

HRID 1975641 reaction equation
[N+]([O-])(O)=[O:2].[CH3:5][C:6]1([CH3:15])[CH2:11][CH2:10][CH2:9][C@H:8]([CH3:12])[C@H:7]1[CH:13]=[O:14]>>[CH3:15][C:6]1([CH3:5])[CH2:11][CH2:10][CH2:9][C@H:8]([CH3:12])[C@H:7]1[C:13]([OH:2])=[O:14]

Participants

3

Reactant 2

HCID 944Nitric AcidHCID 11607949rel-(1R,6S)-2,2,6-Trimethylcyclohexanecarboxaldehyde

Product 1

HCID 11355731(1R,6S)-2,2,6-Trimethylcyclohexanecarboxylic acidYield 98.5%

Conditions

Temperature
55 °C

Procedure

In a 300-ml 4-necked flask equipped with a condenser, a thermometer, a dropping funnel, and a stirrer was placed 42 g of nitric acid (aqueous 60% solution), and the temperature was raised to 55° C. by heating. To the solution was added dropwise 100 g (0.65 mole) of (1R,6S)-2,2,6-trimethylcyclohexanecarbaldehyde (10) [composition: 90% of the (1R,6S)-form, 10% of the (1S,6S)-form] synthesized in Synthetic Example 4-A) with stirring over a period of 2 hours. After carrying out the reaction for 3 hours at the same temperature, the reaction mixture was washed with water with 100 g of toluene and 100 g of water at room temperature, followed by separating an organic layer from an aqueous layer. The organic layer was washed thrice with 100 g of a saturated aqueous sodium chloride solution, followed by separating the organic layer from an aqueous layer. The toluene was distilled off from the organic layer by an evaporator under reduced pressure to provide 109 g of crude (1R,6S)-2,2,6-trimethylcyclohexanecarboxylic acid (11) [composition: 91% of the (1R,6S)-form, 9% of the (1S,6S)-form; melting point: 44° C. to 54° C⟧

Workup

  1. customIn a 300-ml 4-necked flask equipped with a condenser
  2. temperatureby heating
  3. custom90% of the (1R,6S)-form, 10% of the (1S,6S)-form] synthesized in Synthetic Example 4-A)
  4. customthe reaction for 3 hours at the same temperature
  5. washthe reaction mixture was washed with water with 100 g of toluene and 100 g of water at room temperature
  6. customby separating an organic layer from an aqueous layer
  7. washThe organic layer was washed thrice with 100 g of a saturated aqueous sodium chloride solution
  8. customby separating the organic layer from an aqueous layer
  9. distillationThe toluene was distilled off from the organic layer by an evaporator under reduced pressure

Sources & evidence

ORD record
ord-71e3ed0803944e9babd844536beab9e4
Source dataset
uspto-grants-1994_02
Patent number
US05288702

Reaction notes

Loading…