4-Nitrobenzoic Acid → Menthol

HRID 551739Notes

Reaction equation

HRID 551739 reaction equation
[CH3:1][C@H:2]1[CH2:7][C@@H:6]([OH:8])[C@H:5]([CH:9]([CH3:11])[CH3:10])[CH2:4][CH2:3]1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.[N+:31]([C:34]1[CH:42]=[CH:41][C:37]([C:38]([OH:40])=[O:39])=[CH:36][CH:35]=1)([O-:33])=[O:32].COCCOC(N=NC(OCCOC)=O)=O>C1COCC1.O>[N+:31]([C:34]1[CH:35]=[CH:36][C:37]([C:38]([O:40][C@@:6]2([OH:8])[CH2:7][C@H:2]([CH3:1])[CH2:3][CH2:4][C@H:5]2[CH:9]([CH3:11])[CH3:10])=[O:39])=[CH:41][CH:42]=1)([O-:33])=[O:32].[CH:2]1([CH3:1])[CH2:3][CH2:4][CH:5]([CH:9]([CH3:10])[CH3:11])[CH:6]([OH:8])[CH2:7]1

Participants

8

Reactant 4

HCID 61084-Nitrobenzoic AcidHCID 11776TriphenylphosphineHCID 16666(-)-MentholHCID 533844152-methoxyethyl N-(2-methoxyethoxycarbonylimino)carbamate

Product 2

HCID 1254MentholHCID 66919594HCID 66919594, compound

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 8028TetrahydrofuranSolvent2×

Procedure

After L-menthol (300 mg, 1.92 mmol), triphenylphosphine (605 mg, 2.30 mmol), 4-nitrobenzoic acid (385 mg, 2.30 mmol), and THF (12 ml) were added to a 50 ml flask, azodicarboxylic acid bis(2-methoxyethyl) ester (540 mg, 2.30 mmol) dissolved in THF (6 ml) was added dropwise thereto at 20° C., and the reaction was allowed to proceed for 17 hours. Water (0.5 ml) was added, and concentration was carried out. Then, water (10 ml) was added to the solution, and extraction was carried out using diethyl ether (10 ml, ×2). Then, the organic layer was washed with water (10 mL) and saturated salt water (10 ml), and dehumidified with anhydrous magnesium sulfate. Subsequently, a crude product obtained by concentration was purified by column chromatography (silica gel, 5% ethyl acetate-hexane solution) to give (1S,2S,5R)-1-(4-nitrobenzoyloxy)-2-isopropyl-5-methyl cyclohexanol as a white solid substance (430 mg, yield: 73%/L-menthol).

Workup

  1. additionwas added dropwise
  2. customat 20° C.
  3. concentrationconcentration
  4. additionThen, water (10 ml) was added to the solution, and extraction
  5. washThen, the organic layer was washed with water (10 mL) and saturated salt water (10 ml)
  6. customSubsequently, a crude product obtained by concentration
  7. customwas purified by column chromatography (silica gel, 5% ethyl acetate-hexane solution)

Sources & evidence

ORD record
ord-953c58686a1043f29bb01cb44e2d242c
Source dataset
uspto-grants-2011_05
Patent number
US07947816B2

Reaction notes

Loading…