alpha-Hydroxyacetophenone → Monomethyl terephthalate

HRID 1650905Notes

Reaction equation

HRID 1650905 reaction equation
OCC(C1C=CC=CC=1)=O.[Cl-].[CH3:12][O:13][C:14](=[O:24])[C:15]1[CH:23]=[CH:22][C:18]([C:19]([OH:21])=[O:20])=[CH:17][CH:16]=1>N1C=CC=CC=1.C(OCC)(=O)C>[CH3:12][O:13][C:14](=[O:24])[C:15]1[CH:23]=[CH:22][C:18]([C:19]([OH:21])=[O:20])=[CH:17][CH:16]=1

Participants

5

Reactant 2

HCID 68490alpha-HydroxyacetophenoneHCID 53442854Terephthalic acid monomethylester chloride

Product 1

HCID 15513Monomethyl terephthalateYield 82.8%

Reagents, catalysts & solvents 2

HCID 1049PyridineSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of the thus-obtained 112 mg of 2-hydroxyacetophenone in 10 ml of pyridine was added 300 mg of terephthalic acid monomethyl ester chloride and the mixture stirred at room temperature for one night. The reaction mixture was diluted with ethyl acetate and washed with water, Cu(NO3) 0.2aq, water, sodium bicarbonate solution, saturated saline solution and dried over MgSO4. The distillation of the solvent and purification by chromatography through silica gel column gave 161 mg (yield: 82.8%) of the derivative of terephthalic acid methylester. To a solution of 257 mg of the thus-obtained methylester in 5 ml of pyridine was added 75 mg of caustic potash and the mixture stirred at room temperature for one night. The reaction mixture was poured over 20 ml of 20% acetic acid and extracted in ethyl acetate. The resulting organic layer was washed with water 2-3 times and dried over MgSO4. The distillation of the solvent and purification by chromatography through silica gel column gave 135 mg (yield: 62.8%) of the rearranged product (IV, R1, R2 =(CH3)2CCH2CH2O, R3 =CH3, as orange needles having a melting point of 193°-195.5° C. (CH2Cl2 -hexane).

Workup

  1. washwashed with water, Cu(NO3) 0.2aq, water, sodium bicarbonate solution, saturated saline solution
  2. dry with materialdried over MgSO4
  3. distillationThe distillation of the solvent and purification by chromatography through silica gel column

Sources & evidence

ORD record
ord-941685fcfc3142c0afdca3461c1fff5b
Source dataset
uspto-grants-1990_05
Patent number
US04925979

Reaction notes

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