Potassium Hydroxide → 4-Tert-butoxy-3-methoxy-benzoic acid

HRID 1908082Notes

Reaction equation

HRID 1908082 reaction equation
[C:1]([O:5][C:6]1[CH:13]=[CH:12][C:9]([CH:10]=[O:11])=[CH:8][C:7]=1[O:14][CH3:15])([CH3:4])([CH3:3])[CH3:2].[OH-].[K+].[O-:18][Mn](=O)(=O)=O.[K+]>O1CCOCC1>[C:1]([O:5][C:6]1[CH:13]=[CH:12][C:9]([C:10]([OH:18])=[O:11])=[CH:8][C:7]=1[O:14][CH3:15])([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 3

HCID 14797Potassium HydroxideHCID 516875Potassium PermanganateHCID 154394174-Tert-butoxy-3-methoxybenzaldehyde

Product 1

HCID 585512294-Tert-butoxy-3-methoxy-benzoic acidYield 49%

Reagents, catalysts & solvents 1

HCID 312751,4-DioxaneSolvent

Procedure

4-tert-Butoxy-3-methoxybenzaldehyde (130 mg, 0.62 mmol) was suspended in a mixture of dioxane (520 μL) and potassium hydroxide (6.5 mL of 0.20 M, 1.3 mmol). KMnO4 (150 mg, 0.93 mmol) was added and the reaction was stirred vigorously for 16 h. The reaction mixture was filtered and then concentrated to 3 mL. Hydrochloric acid (1M, 4 mL) was added and the resulting precipitate was filtered (after standing for 15 minutes) and washed with 1M HCl and a small amount of water to yield 4-tert-butoxy-3-methoxy-benzoic acid (68 mg, 49%) as a white solid. Rf=0.23 (SiO2, 40% ethyl acetate in hexanes); ESI-MS m/z calc. 224.1. found 225.2 (M+1)+. Retention time: 1.66 minutes (3 min run). 1H NMR (400 MHz, DMSO) δ 12.80 (s, 1H), 7.66-7.41 (m, 2H), 7.09 (d, J=8.8 Hz, 1H), 3.78 (s, 3H), 1.32 (s, 9H). The following compounds were synthesized using the procedures described above: 4-tert-butoxy-3-methylbenzoic acid from 4-hydroxy-3-methylbenzaldehyde, 2-fluoro-4,5-dimethoxybenzoic acid from 2-fluoro-4,5-dimethoxybenzaldehyde, 4-tert-butoxy-2-methoxybenzoic acid from 4-hydroxy-2-methoxybenzaldehyde, 4-tert-butoxy-2-fluorobenzoic acid from 2-fluoro-4-hydroxybenzaldehyde, and 4-tert-butoxybenzoic acid from 4-hydroxybenzaldehyde.

Workup

  1. filtrationThe reaction mixture was filtered
  2. concentrationconcentrated to 3 mL
  3. additionHydrochloric acid (1M, 4 mL) was added
  4. filtrationthe resulting precipitate was filtered (after standing for 15 minutes)
  5. washwashed with 1M HCl

Sources & evidence

ORD record
ord-a285dfe53d0e4329847bf61633e5fce7
Source dataset
uspto-grants-2013_12
Patent number
US08598164B2

Reaction notes

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