4-Nitrobenzoic Acid → Menthol

HRID 1162878Notes

Reaction equation

HRID 1162878 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].C(OC(N=NC(OC(C)C)=O)=O)(C)C.C1(C)C=CC=CC=1>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 66880968DIAD toluene

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 (387 mg, 2.30 mmol), and THF (12 ml) were added to a 50 ml flask, a 40% azodicarboxylic acid diisopropyl ester-toluene solution (1.21 ml, 2.30 mmol) dissolved in THF (6 ml) was added dropwise thereto at 20° C., and the reaction was allowed to proceed for 15 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 (423 mg, yield: 72%/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-61d3aff3ab804e6a9a0a6c5be8772596
Source dataset
uspto-grants-2010_10
Patent number
US07820802B2

Reaction notes

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