Chloroacetaldehyde → Methyl 2-methylfuran-3-carboxylate

HRID 2058125Notes

Reaction equation

HRID 2058125 reaction equation
N[C@H:2]([C:6]([OH:8])=[O:7])[CH:3]([CH3:5])C.N1C=CC=C[CH:10]=1.Cl[CH2:16][CH:17]=[O:18].Cl>>[CH3:10][O:8][C:6]([C:2]1[CH:3]=[CH:5][O:18][C:17]=1[CH3:16])=[O:7]

Participants

5

Reactant 4

HCID 33ChloroacetaldehydeHCID 313Hydrochloric AcidHCID 1049PyridineHCID 6287L-Valine

Product 1

HCID 80237Methyl 2-methylfuran-3-carboxylate

Conditions

Temperature
70 °C

Procedure

58.055 kg (500 mol) acetacetic acid methyl ester are introduced into a vessel with a stirrer and 22.5 kg (487.5 Val) of ground dolomite having a grain size of 30 μm are mixed therewith. Then 0.988 kg (12.5 mol=2.5 mol%) pyridine are added thereto and the mixture is heated to 70° C., whereupon 87.2 kg (500 mol) 45% aqueous chloracetaldehyde solution are metered in within one hour. The temperature in the reaction is maintained at 70° C. by slight cooling. About 4 hours after the onset of the reaction, light heating is required; after 6-7 hours, heating to 75°-80° C. is performed, and thereafter heating is discontinued and stirring is continued for some time at falling temperatures. To the reaction mixture cooled to room temperature, concentrated hydrochloric acid is added in portions in order to decompose excessive dolomite. After separation of phases the aqueous bottom layer is removed and the organic layer washed with 76 liters of water. For better phase separation, about 2 kg. salt are added. The organic phase, which is now the bottom phase, is separated and distilled under reduced pressure. The yield in 2-methyl-3-carboxylic acid methyl ester amounts to 53.6 kg=76.6% of the theoretical amount.

Workup

  1. customare metered in within one hour
  2. customAbout 4 hours after the onset of the reaction
  3. temperaturelight heating
  4. temperatureheating to 75°-80° C.
  5. temperatureheating
  6. temperatureTo the reaction mixture cooled to room temperature
  7. customAfter separation of phases the aqueous bottom layer
  8. customis removed
  9. washthe organic layer washed with 76 liters of water
  10. customFor better phase separation, about 2 kg
  11. additionsalt are added
  12. customis separated
  13. distillationdistilled under reduced pressure
  14. customThe yield in 2-methyl-3-carboxylic acid methyl ester

Sources & evidence

ORD record
ord-0f5b7b89a11445aebdeb6e2fb33f639c
Source dataset
uspto-grants-1980_07
Patent number
US04215057

Reaction notes

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