Formic Acid → Diethyl 5-methylpyridine-2,3-dicarboxylate

HRID 1074233Notes

Reaction equation

HRID 1074233 reaction equation
C(O)=O.[CH3:4][C:5](=[CH2:8])[CH:6]=O.[NH2:9][C:10]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH:11][C:12]([O:14][CH2:15][CH3:16])=[O:13]>C(O)(C)C>[CH3:8][C:5]1[CH:4]=[C:11]([C:12]([O:14][CH2:15][CH3:16])=[O:13])[C:10]([C:17]([O:19][CH2:20][CH3:21])=[O:18])=[N:9][CH:6]=1

Participants

5

Reactant 3

HCID 284Formic AcidHCID 6562MethacroleinHCID 71360915Diethyl 2-aminobut-2-enedioate

Product 1

HCID 11806659Diethyl 5-methylpyridine-2,3-dicarboxylateYield 50%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
70 °C

Procedure

Isopropyl alcohol 675 ml and 90% formic acid 61.5 g (1.20 mol) were placed in 1 liter four-neck flask equipped with a reflux condenser. After heating the content to 70° C., 2-methyl-2-propenal 84.3 g (1.20 mol) and ethyl β-amino-β-ethoxycarbonylacrylate 150 g (0.801 mol) were simultaneously added dropwise thereto over a period of 1 hour with air-bubbling and refluxed for 10 hours. After removing isopropyl alcohol, 400 ml of water was added thereto and neutralized with sodium bicarbonate. After standing at 65°-67° C., separated oil layer was concentrated under reduced pressure to obtain 200 g of oily substance, which was distilled under reduced pressure to give 95 g of 5-methyl-2,3-diethoxycarbonylpyridine.

Workup

  1. customequipped with a reflux condenser
  2. customover a period of 1 hour with air-bubbling
  3. temperaturerefluxed for 10 hours
  4. customAfter removing isopropyl alcohol, 400 ml of water
  5. additionwas added
  6. customAfter standing at 65°-67° C.
  7. customseparated oil layer
  8. concentrationwas concentrated under reduced pressure
  9. customto obtain 200 g of oily substance, which
  10. distillationwas distilled under reduced pressure

Sources & evidence

ORD record
ord-5983323c9bf04e13a9af915bdecfff58
Source dataset
uspto-grants-1990_11
Patent number
US04973695

Reaction notes

Loading…