Methyl chloroformate → Methyl (2-methylphenyl)(oxo)acetate

HRID 2248984Notes

Reaction equation

HRID 2248984 reaction equation
[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:10])C.[OH-].[K+].[Mn]([O-])(=O)(=O)=O.[K+].S(=O)(O)[O-].[Na+].C(N(CC)CC)C.Cl[C:32]([O:34][CH3:35])=[O:33]>O.ClCCl.N1C=CC=CC=1>[CH3:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:8](=[O:10])[C:32]([O:34][CH3:35])=[O:33]

Participants

10

Reactant 6

HCID 6586Methyl chloroformateHCID 8471TriethylamineHCID 113402-MethylacetophenoneHCID 14797Potassium HydroxideHCID 516875Potassium PermanganateHCID 23665763Sodium Bisulfite

Product 1

HCID 3768392Methyl (2-methylphenyl)(oxo)acetate

Reagents, catalysts & solvents 3

HCID 962WaterSolvent2×HCID 1049PyridineSolventHCID 6344DichloromethaneSolvent

Procedure

1.4 g (10 millimoles) of ortho-methylacetophenone, 2.0 g of potassium hydroxide, 200 ml of pyridine and 100 ml of water are initially taken at +10° C. 5 g of potassium permanganate in 250 ml of water are added dropwise and the mixture is stirred for 2 hours at this temperature. Thereafter, sodium bisulfite solution is added dropwise until the red coloration of the mixture vanishes. The mixture is filtered, the filtrate is acidified with concentrated hydrochloric acid and filtered again and this filtrate is extracted with 5×50 ml of methyl tert-butyl ether. The organic phase is dried over sodium sulfate and evaporated down and the residue is then directly reacted further (ratio of ketoacid to benzoic acid 8-9:1 according to 1H-NMR). 2.0 g of the above mixture in 20 ml of dichloromethane are initially taken and 1.6 g (16 millimoles) of triethylamine are added. 1.5 g (16 millimoles) of methyl chloroformate are added dropwise at room temperature. After 1 hour at this temperature, the mixture is extracted with phosphate buffer (pH 7) and evaporation and distillation are carried out.

Workup

  1. customare initially taken at +10° C
  2. filtrationThe mixture is filtered
  3. filtrationfiltered again
  4. extractionthis filtrate is extracted with 5×50 ml of methyl tert-butyl ether
  5. dry with materialThe organic phase is dried over sodium sulfate
  6. customevaporated down
  7. customthe residue is then directly reacted further (ratio of ketoacid to benzoic acid 8-9:1 according to 1H-NMR)
  8. waitAfter 1 hour at this temperature
  9. extractionthe mixture is extracted with phosphate buffer (pH 7) and evaporation and distillation

Sources & evidence

ORD record
ord-47ebbd9290044255988dd73f85f25e13
Source dataset
uspto-grants-1991_08
Patent number
US05041618

Reaction notes

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