Hydrochloric Acid → 1-(4-chloro-2,6-dimethylphenyl)ethanone

HRID 1843741Notes

Reaction equation

HRID 1843741 reaction equation
N(OC(C)(C)C)=O.N[C:9]1[CH:14]=[C:13]([CH3:15])[C:12]([C:16](=[O:18])[CH3:17])=[C:11]([CH3:19])[CH:10]=1.[ClH:20]>C(#N)C.[Cu](Cl)Cl>[Cl:20][C:9]1[CH:14]=[C:13]([CH3:15])[C:12]([C:16](=[O:18])[CH3:17])=[C:11]([CH3:19])[CH:10]=1

Participants

6

Reactant 3

HCID 313Hydrochloric AcidHCID 10906Tert-Butyl nitriteHCID 450862771-(4-Amino-2,6-dimethylphenyl)ethan-1-one

Product 1

HCID 534028641-(4-chloro-2,6-dimethylphenyl)ethanoneYield 76%

Reagents, catalysts & solvents 2

HCID 24014Cupric ChlorideCatalystHCID 6342AcetonitrileSolvent

Conditions

Temperature
0 °C

Procedure

Anhydrous copper(II) chloride (98.9 g, 0.74 mol) was mixed with tert-butyl nitrite (94.8 g, 0.83 mol) in acetonitrile (1.02 L). The solution was cooled to 0° C. and slowly added with 1-(4-amino-2,6-dimethylphenyl)ethanone (100 g, 0.61 mol) in a period of 5.0 min. After the addition was completed, the reaction mixture was warmed to room temperature, and was poured into an aqueous hydrochloric acid solution (20%, 1.0 L). The solution was extracted with EtOAc (800 mL), and the organic layer was separated, washed with H2O (1.0 L), dried over MgSO4 (s), and concentrated under reduced pressure. The liquid was distilled to give 1-(4-chloro-2,6-dimethylphenyl)ethanone (85.0 g) as yellow oil in 76% yield: 1H NMR (500 MHz, CDCl3) δ 7.02 (s, 2 H), 2.45 (s, 3 H), 2.22 (s, 6 H).

Workup

  1. additionAfter the addition
  2. temperaturethe reaction mixture was warmed to room temperature
  3. extractionThe solution was extracted with EtOAc (800 mL)
  4. customthe organic layer was separated
  5. washwashed with H2O (1.0 L)
  6. dry with materialdried over MgSO4 (s)
  7. concentrationconcentrated under reduced pressure
  8. distillationThe liquid was distilled

Sources & evidence

ORD record
ord-58c0ffd9bc2145c38f1b5c634e29e6b3
Source dataset
uspto-grants-2015_02
Patent number
US08946268B2

Reaction notes

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