Ethanol → 2-Nitro-α-oxo-4-(phenylmethoxy)benzenepropanoic acid

HRID 987263

Reaction equation

HRID 987263 reaction equation
[O-]CC.[K+].C(O)C.[CH2:8]([O:15][C:16]1[CH:21]=[CH:20][C:19]([CH3:22])=[C:18]([N+:23]([O-:25])=[O:24])[CH:17]=1)[C:9]1[CH:14]=[CH:13][CH:12]=[CH:11][CH:10]=1.[C:26](OCC)(=[O:32])[C:27]([O:29]CC)=[O:28]>C1(C)C=CC=CC=1.C(OCC)C>[CH2:8]([O:15][C:16]1[CH:21]=[CH:20][C:19]([CH2:22][C:26](=[O:32])[C:27]([OH:29])=[O:28])=[C:18]([N+:23]([O-:25])=[O:24])[CH:17]=1)[C:9]1[CH:10]=[CH:11][CH:12]=[CH:13][CH:14]=1

Participants

7

Reactant 4

HCID 702EthanolHCID 7268Diethyl OxalateHCID 28015074-Benzyloxy-2-nitrotolueneHCID 23670592Potassium ethoxide

Product 1

HCID 229886812-Nitro-α-oxo-4-(phenylmethoxy)benzenepropanoic acidYield 89.8%

Reagents, catalysts & solvents 2

HCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Conditions

Temperature
0 °C

Procedure

Potassium ethoxide (505 g; 6 mole) was added to a solution of ethanol (710 ml) and diethyl ether (4.8 l) and the mixture was cooled to 0° C. 4-(Benzyloxy)-1-methyl-2-nitrobenzene (639.8 g; 3 mole) dissolved in diethyl oxalate (900 g; 6.16 mole) and toluene (1500 ml) was added slowly during 30 minutes. The reaction mixture was stirred for 3 hours at 0° C. and then allowed to stand cold over night. After 5 days at room temperature the reaction mixture was filtered and the filter cake was washed with diethyl ether (2 l). The cake was then treated with water (10 l), sodium hydroxide (5 M, 0.8 l) and extracted three times with diethyl ether (3×3 l). The water phase was cooled and acidified in two steps while stirring with hydrochloric acid:water (1:1, 0.9 l). First to pH 5 and the reaction mixture was then stirred for 1 hour before the acidification continued to pH 2. The reaction mixture was cooled in an ice:sodium chloride bath. Filtration after 1 hour gave 849.5 g (89.8%) of 3-(4-benzyloxy-2-nitrophenyl)-2-oxopropanoic acid.

Workup

  1. waitto stand cold over night
  2. filtrationAfter 5 days at room temperature the reaction mixture was filtered
  3. washthe filter cake was washed with diethyl ether (2 l)
  4. additionThe cake was then treated with water (10 l), sodium hydroxide (5 M, 0.8 l)
  5. extractionextracted three times with diethyl ether (3×3 l)
  6. temperatureThe water phase was cooled
  7. stirringwhile stirring with hydrochloric acid:water (1:1, 0.9 l)
  8. stirringFirst to pH 5 and the reaction mixture was then stirred for 1 hour before the acidification
  9. temperatureThe reaction mixture was cooled in an ice
  10. filtrationFiltration after 1 hour

Sources & evidence

ORD record
ord-af73158930884f219dc43e1d3840def5
Source dataset
uspto-grants-2003_10
Patent number
US06630600B1

Linked notes

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