Hydrochloric Acid → Ethyl (2,6-diethyl-4-methylphenyl)glyoxylate

HRID 335401Notes

Reaction equation

HRID 335401 reaction equation
[Mg].BrC(Br)C.[CH2:6]([C:8]1[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([CH2:15][CH3:16])[C:9]=1Br)[CH3:7].[C:18](OCC)(=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20].Cl>O1CCCC1>[CH2:6]([C:8]1[CH:13]=[C:12]([CH3:14])[CH:11]=[C:10]([CH2:15][CH3:16])[C:9]=1[C:18](=[O:24])[C:19]([O:21][CH2:22][CH3:23])=[O:20])[CH3:7]

Participants

7

Reactant 5

HCID 313Hydrochloric Acid2×HCID 7268Diethyl OxalateHCID 112011,1-DibromoethaneHCID 5462224MagnesiumHCID 115794912-Bromo-1,3-diethyl-5-methylbenzene

Product 1

HCID 56942718Ethyl (2,6-diethyl-4-methylphenyl)glyoxylateYield 98.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
30 °C

Procedure

To a 3 L volume four-necked flask, magnesium (cutting chip) (35.31 g) and tetrahydrofuran (anhydrous) (600 ml) were added under a nitrogen atmosphere at room temperature. Once starting to stir, the internal temperature was raised to about 30° C., dibromoethane (25.4 g) was added dropwise over 20 minutes to the mixture. After the resulting mixture was stirred for 30 minutes, the internal temperature was raised to about 50° C. To the mixture was added dropwise 2,6-diethyl-4-methylbromobenzene (10-a) (300.18 g) dissolved in tetrahydrofuran (150 ml) over 2 hours. The resulting mixture was stirred at 50° C. for 1 hour and cooled. To the mixture was added dropwise diethyl oxalate (192.5 g) at about 0° C. over 15 minutes. The resulting mixture was stirred at room temperature for 2 hours. Then, 3.5% by weight of hydrochloric acid (1000 ml) and concentrated hydrochloric acid (60 ml) were added with cooling. After the organic solvent was removed under reduced pressure, the aqueous layer was extracted with tert-butyl methyl ether. The organic layer was concentrated under reduced pressure to give 320.82 g of ethyl 2-(2,6-diethyl-4-methylphenyl)-2-oxoacetate (9-a).

Workup

  1. stirringAfter the resulting mixture was stirred for 30 minutes
  2. temperaturethe internal temperature was raised to about 50° C
  3. stirringThe resulting mixture was stirred at 50° C. for 1 hour
  4. temperaturecooled
  5. stirringThe resulting mixture was stirred at room temperature for 2 hours
  6. temperaturewith cooling
  7. customAfter the organic solvent was removed under reduced pressure
  8. extractionthe aqueous layer was extracted with tert-butyl methyl ether
  9. concentrationThe organic layer was concentrated under reduced pressure

Sources & evidence

ORD record
ord-cbb29ede11624f17b9d91806dc80d74e
Source dataset
uspto-grants-2014_11
Patent number
US08884010B2

Reaction notes

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