Methanol → Methyl phenylglyoxalate

HRID 1982586Notes

Reaction equation

HRID 1982586 reaction equation
[C:1]([C:9]#N)(=[O:8])[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[CH3:11][O:12]C(=O)C1C=CC=CC=1.S(=O)(=O)(O)[OH:22].CO>O.C(Cl)(=O)C>[CH3:11][O:12][C:9](=[O:22])[C:1]([C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)=[O:8]

Participants

7

Reactant 4

HCID 887MethanolHCID 1118Sulfuric AcidHCID 7150Methyl BenzoateHCID 11953Phenylglyoxylonitrile

Product 1

HCID 84835Methyl phenylglyoxalateYield 194.2%

Reagents, catalysts & solvents 2

HCID 6367Acetyl chlorideCatalystHCID 962WaterSolvent2×

Procedure

A mixture of 393 g (3 mol) of benzoyl cyanide, 20.3 g (0.26 mol) of acetyl chloride and 202 g of benzoic acid methyl ester was added dropwise, at 22° C., to 450 g (4.6 mol) of concentrated sulphuric acid. The mixture was subsequently stirred for one hour and 72 g (4 mol) of water were then added at 22° C. in the course of about 20 minutes. The mixture was then stirred for a further 3 hours at 22° C. 304 g (9.5 mols) of methanol were added to the reaction mixture and the mixture was stirred for 3 hours at about 70° C. After cooling, the reaction mixture was diluted with 390 g of water. The organic phase was separated off and washed successively with 160 g of water, 160 g of sodium bicarbonate solution and 160 g of water. The combined aqueous phases were extracted twice with 30 ml of toluene each time. The organic phases were combined, and concentrated by distilling off the solvent. Distillation of the residue gave 473 g (96% of theory) of phenylglyoxylic acid methyl ester, which had a boiling point of 136° C./12 mm Hg and a purity of 99% (determined by gas chromatography).

Workup

  1. stirringThe mixture was then stirred for a further 3 hours at 22° C
  2. stirringthe mixture was stirred for 3 hours at about 70° C
  3. temperatureAfter cooling
  4. customThe organic phase was separated off
  5. washwashed successively with 160 g of water, 160 g of sodium bicarbonate solution and 160 g of water
  6. extractionThe combined aqueous phases were extracted twice with 30 ml of toluene each time
  7. concentrationconcentrated
  8. distillationby distilling off the solvent
  9. distillationDistillation of the residue

Sources & evidence

ORD record
ord-db1031dbf120455daa68b40b0990ec12
Source dataset
uspto-grants-1986_06
Patent number
US04596885

Reaction notes

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