4-Chloroaniline → (4-Chloro-phenyl)-(neopentyl)-amine

HRID 964711Notes

Reaction equation

HRID 964711 reaction equation
[CH:1](=O)[C:2]([CH3:5])([CH3:4])[CH3:3].[Cl:7][C:8]1[CH:14]=[CH:13][C:11]([NH2:12])=[CH:10][CH:9]=1.[BH4-].[Na+]>C(O)(=O)C.O>[Cl:7][C:8]1[CH:14]=[CH:13][C:11]([NH:12][CH2:1][C:2]([CH3:5])([CH3:4])[CH3:3])=[CH:10][CH:9]=1

Participants

6

Reactant 3

HCID 78124-ChloroanilineHCID 12417PivalaldehydeHCID 4311764Sodium borohydride

Product 1

HCID 11424155(4-Chloro-phenyl)-(neopentyl)-amineYield 101.2%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolventHCID 962WaterSolvent

Conditions

Temperature
0 °C

Procedure

Pivalaldehyde (20.4 g, 236 mmol, 25.6 mL) was added to a solution of 4-chloroaniline (30.2 g, 236 mmol) in concentrated acetic acid (475 mL) at ambient temperature. After 1.5 hour, the reaction mixture was cooled to 0° C. and sodium borohydride (11.7 g, 307 mmol) was added portionwise over 15 minutes After stirring for 1 hour, the resulting mixture was diluted with water and extracted with ethyl acetate (3×). The combined organics were washed successively with water (3×), aqueous 2N sodium hydroxide (2×), saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride, dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure to give 47.2 g (99%) of the title compound as an off-white solid which was taken on crude to the next step.

Workup

  1. extractionextracted with ethyl acetate (3×)
  2. washThe combined organics were washed successively with water (3×), aqueous 2N sodium hydroxide (2×), saturated aqueous sodium bicarbonate, and saturated aqueous sodium chloride
  3. dry with materialdried over anhydrous sodium sulfate
  4. filtrationfiltered
  5. concentrationconcentrated under reduced pressure

Sources & evidence

ORD record
ord-911dcf046cd246e3ae6c1bf95a017eba
Source dataset
uspto-grants-1998_06
Patent number
US05770594

Reaction notes

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