Sodium Iodide → N-ethoxycarbonylmethyl-N-isopropyl aniline

HRID 1582757Notes

Reaction equation

HRID 1582757 reaction equation
[CH:1]([NH:4][C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)([CH3:3])[CH3:2].Br[CH2:12][C:13]([O:15][CH2:16][CH3:17])=[O:14].C(=O)([O-])[O-].[K+].[K+].[I-].[Na+]>CN(C)C=O>[CH2:16]([O:15][C:13]([CH2:12][N:4]([CH:1]([CH3:3])[CH3:2])[C:5]1[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1)=[O:14])[CH3:17]

Participants

6

Reactant 4

HCID 5238Sodium IodideHCID 7748Ethyl bromoacetateHCID 11430Potassium CarbonateHCID 13032N-Isopropylaniline

Product 1

HCID 71006187N-ethoxycarbonylmethyl-N-isopropyl anilineYield 99%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

N-isopropyl aniline 1.0 g, ethyl bromoacetate 2.47 g, potassium carbonate 5.11 g and sodium iodide 5.55 g were dissolved in N,N-dimethylformamide 14 ml in a nitrogen atmosphere and stirred under reflux with heating. After 1 hour, the reaction mixture was cooled to room temperature and then partitioned by adding water and diethyl ether, and the organic layer was washed with water and then with brine, dried over magnesium sulfate anhydride, and evaporated. The residue was purified by silica gel column chromatography (hexane/diethyl ethersystem) to give N-ethoxycarbonylmethyl-N-isopropyl aniline 1.62 g. A part 550 mg of this product was dissolved in tetrahydrofuran 10 ml, and 1M lithium aluminum hydride in tetrahydrofuran 2.5 ml was added thereto under cooling in an ice bath in a nitrogen atmosphere. The mixture was stirred in the ice bath for 40 minutes, and water 0.1 ml, 2N aqueous sodium hydroxide 0.1 ml, water 0.3 ml, and diethyl ether 5 ml were added in this order and stirred. The insolubles were filtered off through Celite, and the filtrate was evaporated. The residue was purified by silica gel column chromatography (hexane/ethyl acetate system), whereby the title compound 383 mg, 86% was obtained as a colorless oil.

Workup

  1. temperatureunder reflux
  2. temperaturewith heating
  3. custompartitioned
  4. additionby adding water and diethyl ether
  5. washthe organic layer was washed with water
  6. dry with materialwith brine, dried over magnesium sulfate anhydride
  7. customevaporated
  8. customThe residue was purified by silica gel column chromatography (hexane/diethyl ethersystem)

Sources & evidence

ORD record
ord-6bb1681912f84691a315388203f4d5ae
Source dataset
uspto-grants-2004_05
Patent number
US06737425B1

Reaction notes

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