Ethyl pyruvate → 1-(2-Amino-5-bromophenyl)ethan-1-one

HRID 2423519Notes

Reaction equation

HRID 2423519 reaction equation
[Sn](Cl)Cl.[Br:4][C:5]1[CH:6]=[CH:7][C:8]([N+:14]([O-])=O)=[C:9]([C:11](=[O:13])[CH3:12])[CH:10]=1.[C:17]([O:22][CH2:23][CH3:24])(=[O:21])[C:18]([CH3:20])=O>C(OCC)C.C(O)C.[Cl-].[Zn+2].[Cl-]>[Br:4][C:5]1[CH:10]=[C:9]2[C:8](=[CH:7][CH:6]=1)[N:14]=[C:18]([C:17]([O:22][CH2:23][CH3:24])=[O:21])[CH:20]=[C:11]2[CH3:12].[Br:4][C:5]1[CH:6]=[CH:7][C:8]([NH2:14])=[C:9]([C:11](=[O:13])[CH3:12])[CH:10]=1

Participants

8

Reactant 3

HCID 12041Ethyl pyruvateHCID 24479Stannous ChlorideHCID 122241571-(5-Bromo-2-nitrophenyl)ethanone

Product 2

HCID 110747461-(2-Amino-5-bromophenyl)ethan-1-oneYield 62%HCID 59321550HCID 59321550, compoundYield 3%

Reagents, catalysts & solvents 3

HCID 3007855ZincchlorideCatalystHCID 702EthanolSolvent2×HCID 3283Diethyl EtherSolvent

Conditions

Temperature
70 °C

Procedure

A 2.2 M solution of zinc(II)chloride (9.31 mL, 20.49 mmol) in diethyl ether was added to tin(II)chloride (3.88 g, 20.49 mmol) and activated 4 Å molecular sieve pellets (1.00 g) in ethanol (10 mL) under argon. Then, 1-(5-bromo-2-nitrophenyl)-ethanone (1.00 g, 4.10 mmol) and ethyl pyruvate (499.6 mg, 4.30 mmol) in ethanol (10 mL) were added to the reaction mixture via canula. The mixture was heated at 70° C. in an oil bath for three hours, then allowed to cool to room temperature, and carefully quenched with saturated sodium bicarbonate. Ethyl acetate was added and the mixture was filtered through Celite®. The filtrate was extracted with ethyl acetate and the organic layer was dried over anhydrous magnesium sulfate, then filtered and concentrated. The residue was purified by silica gel chromatography eluting with 1:6 ethyl acetate:hexanes to give 39.4 mg (3%) of ethyl 6-bromo-4-methyl-2-quinolinecarboxylate as a solid and 543.1 mg (62%) of 1-(5-bromo-2-aminophenyl)-ethanone as a solid.

Workup

  1. temperatureto cool to room temperature
  2. customcarefully quenched with saturated sodium bicarbonate
  3. additionEthyl acetate was added
  4. filtrationthe mixture was filtered through Celite®
  5. extractionThe filtrate was extracted with ethyl acetate
  6. dry with materialthe organic layer was dried over anhydrous magnesium sulfate
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customThe residue was purified by silica gel chromatography
  10. washeluting with 1:6 ethyl acetate

Sources & evidence

ORD record
ord-eee7f25649d245efaf646cc8176d4018
Source dataset
uspto-grants-2011_06
Patent number
US07960552B2

Reaction notes

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