3-Nitrobenzaldehyde → ST51002545

HRID 2412870Notes

Reaction equation

HRID 2412870 reaction equation
[N+:1]([C:4]1[CH:5]=[C:6]([CH:9]=[CH:10][CH:11]=1)[CH:7]=O)([O-:3])=[O:2].[C:12]([O:18][CH3:19])(=[O:17])[CH2:13][C:14]([CH3:16])=[O:15]>C(OCC)(=O)C.[Cl-].[Zn+2].[Cl-]>[CH3:19][O:18][C:12]([CH:13]([CH:7]([C:6]1[CH:9]=[CH:10][CH:11]=[C:4]([N+:1]([O-:3])=[O:2])[CH:5]=1)[CH:13]([C:12]([O:18][CH3:19])=[O:17])[C:14](=[O:15])[CH3:16])[C:14](=[O:15])[CH3:16])=[O:17]

Participants

5

Reactant 2

HCID 74493-NitrobenzaldehydeHCID 7757Methyl acetoacetate

Product 1

HCID 4248905ST51002545Yield 49.3%

Reagents, catalysts & solvents 2

HCID 3007855ZincchlorideCatalystHCID 8857Ethyl AcetateSolvent

Procedure

To a mixture of 72.1 g of zinc chloride in 200 ml of ethyl acetate was added dropwise a mixture of 40.0 g of m-nitrobenzaldehyde and 61.5 g of methyl acetoacetate at room temperature over 50 minutes. The mixture was stirred at room temperature for further 15 minutes, and further stirred while heating at 60°-65° C. for 6.5 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, then 800 ml of ether and 800 ml of water were added thereto, and the desired product was extracted with ether. The aqueous layer was extracted again with 300 ml of ether, which was combined with the first ether layer. The combined layer was washed with 200 ml of a 5% aqueous sodium bicarbonate solution, and then with 200 ml of saturated saline. This substance was dried over anhydrous magnesium sulfate, and the ether was distilled off to obtain 92.7 g of crude crystals. The crystals were recrystallized from methanol to obtain 47.7 g (yield 49.3%) of 3,5-bis(methoxycarbonyl)-4-(3-nitrophenyl)-2,6-heptanedione.

Workup

  1. additionwas added dropwise
  2. stirringfurther stirred
  3. temperaturewhile heating at 60°-65° C. for 6.5 hours
  4. customAfter completion of the reaction
  5. concentrationthe reaction mixture was concentrated under reduced pressure
  6. addition800 ml of ether and 800 ml of water were added
  7. extractionthe desired product was extracted with ether
  8. extractionThe aqueous layer was extracted again with 300 ml of ether, which
  9. washThe combined layer was washed with 200 ml of a 5% aqueous sodium bicarbonate solution
  10. dry with materialThis substance was dried over anhydrous magnesium sulfate
  11. distillationthe ether was distilled off
  12. customto obtain 92.7 g of crude crystals
  13. customThe crystals were recrystallized from methanol

Sources & evidence

ORD record
ord-9480154eb46a40de94e61717d9ba9506
Source dataset
uspto-grants-1985_01
Patent number
US04495192

Reaction notes

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