3,4-Dichloroaniline → 3',4'-Dichloro-2,2-dimethylpropionanilide

HRID 396279

Reaction equation

HRID 396279 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:6]=[CH:7][C:8]=1[Cl:9])[NH2:5].[OH-].[Na+].[CH3:12][C:13]([CH3:18])([CH3:17])[C:14](Cl)=[O:15]>CC(OC)(C)C>[Cl:1][C:2]1[CH:3]=[C:4]([NH:5][C:14](=[O:15])[C:13]([CH3:18])([CH3:17])[CH3:12])[CH:6]=[CH:7][C:8]=1[Cl:9]

Participants

5

Reactant 3

HCID 72573,4-DichloroanilineHCID 14798Sodium HydroxideHCID 62493Pivaloyl chloride

Product 1

HCID 1389493',4'-Dichloro-2,2-dimethylpropionanilideYield 86%

Reagents, catalysts & solvents 1

HCID 15413tert-Butyl methyl etherSolvent

Conditions

Temperature
32.5 °C

Procedure

3,4-dichloroaniline (150 g) in TBME (1L) was cooled to 10-15° C. 30% aq NaOH (141 g, 1.14 equiv) was added, and the solution stirred vigorously via overhead mechanical stirrer. Trimethylacetyl chloride (“PivCl”, 126 mL) was added at such a rate as to keep the internal temperature below 30° C. During this addition, the solution mixture becomes thick with white solid product. When the addition was complete (10-15 min), the mixture was heated to 30-35° C. for 1 hr, and then allowed to cool. The reaction mixture was held at −5° C. (overnight), and then filtered, rinsing first with 90:10 water/MeOH (600 mL) and then water (900 mL). Drying under vacuum yielded 195 g (86%) product, as off-white crystals. LCMS m/z 246(M−H)+.

Workup

  1. customthe internal temperature below 30° C
  2. additionDuring this addition
  3. additionWhen the addition
  4. custom(10-15 min)
  5. temperatureto cool
  6. customwas held at −5° C.
  7. custom(overnight)
  8. filtrationfiltered
  9. washrinsing first with 90:10 water/MeOH (600 mL)
  10. customDrying under vacuum

Sources & evidence

ORD record
ord-0166a8e1c5b94af8b27adee8c423576a
Source dataset
uspto-grants-2003_08
Patent number
US06608077B2

Linked notes

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