Hydrochloric Acid → 3-Chloro-2-hydroxy-6-methylbenzaldehyde

HRID 2076581Notes

Reaction equation

[CH2:1]=[O:2].[Cl-].[Mg+2].[Cl-].[Cl:6][C:7]1[CH:12]=[CH:11][C:10]([CH3:13])=[CH:9][C:8]=1[OH:14].Cl>C(#N)C.C(N(CC)CC)C>[Cl:6][C:7]1[C:8]([OH:14])=[C:9]([C:10]([CH3:13])=[CH:11][CH:12]=1)[CH:1]=[O:2]

Participants

Conditions

Temperature: 90 °C

Procedure

Paraformaldehyde (4.73 g, 163 mmol), magnesium chloride (7.76 g, 81.7 mmol) and triethylamine (14.2 ml, 102 mmol were added to a solution of 2-chloro-5-methylphenol (5.80 g, 40.8 mmol) in acetonitrile (100 ml) and the mixture was vigorously stirred at 90° C. for 10 hours. The reaction mixture was poured into 1N hydrochloric acid and extracted with ethyl acetate. After the organic layer was successively washed with 1N hydrochloric acid, water and a saturated aqueous NaCl solution and dried with anhydrous sodium sulfate, it was concentrated under reduced pressure. The obtained residue was subjected to silica gel column chromatography (eluting solvent: hexane/ethyl acetate=3/1) to give crude 3-chloro-2-hydroxy-6-methylbenzaldehyde. According to a method similar to Example (28-3) and Example (28-4), from the crude compound obtained in the above, tert-butyl 2-[(tert-butoxycarbonyl)oxy]-3-chloro-6-methylbenzoate was obtained (1.82 g, three-step total yield: 13%).

Workup

extractionextracted with ethyl acetate
washAfter the organic layer was successively washed with 1N hydrochloric acid, water
dry with materiala saturated aqueous NaCl solution and dried with anhydrous sodium sulfate, it
concentrationwas concentrated under reduced pressure
washThe obtained residue was subjected to silica gel column chromatography (eluting solvent: hexane/ethyl acetate=3/1)

Sources & evidence

ORD record: ord-2faf30d79901402cb4a38559ef3612ce
Source dataset: uspto-grants-2011_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07923573B2

Reaction notes

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