Methanol → Tert-butyl [2-(3,4-dichlorobenzylamino)-1,1-dimethylethyl]carbamate

HRID 1349458Notes

Reaction equation

HRID 1349458 reaction equation
[Cl:1][C:2]1[CH:3]=[C:4]([CH:20]=[CH:21][C:22]=1[Cl:23])[CH2:5][NH:6][C:7]([C:9]([NH:12][C:13](=[O:19])[O:14][C:15]([CH3:18])([CH3:17])[CH3:16])([CH3:11])[CH3:10])=O.B.O1CCCC1.CO>O1CCCC1>[C:15]([O:14][C:13](=[O:19])[NH:12][C:9]([CH3:11])([CH3:10])[CH2:7][NH:6][CH2:5][C:4]1[CH:20]=[CH:21][C:22]([Cl:23])=[C:2]([Cl:1])[CH:3]=1)([CH3:18])([CH3:16])[CH3:17]

Participants

5

Reactant 3

HCID 887MethanolHCID 2723981Borane;tetrahydrofuranHCID 58859130Tert-butyl [1-(3,4-dichlorobenzylcarbamoyl)-1-methylethyl]carbamate

Product 1

HCID 21091376Tert-butyl [2-(3,4-dichlorobenzylamino)-1,1-dimethylethyl]carbamate

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
0 °C

Procedure

The crude crystals (1.0 g) of tert-butyl [1-(3,4-dichlorobenzylcarbamoyl)-1-methylethyl]carbamate obtained in the previous step was dissolved in tetrahydrofuran (5 ml) and cooled to 0° C. under an argon atmosphere. A borane-tetrahydrofuran complex (1.0 M/tetrahydrofuran solution) (15 ml) was added dropwise at the same temperature, removed from an ice-bath and stirred at room temperature for 2 hr. A borane-tetrahydrofuran complex (1.0 M/tetrahydrofuran solution) (5 ml) was added every 30 minutes twice in total. To the obtained reaction mixture was added methanol (10 ml) under ice-cooling, and the solvent was evaporated. The obtained residue was dissolved in tetrahydrofuran (10 ml) and 1N aqueous sodium hydroxide solution (4 ml) and the mixture was stirred at 90° C. for 1 hr. The obtained reaction mixture was extracted twice with toluene, and the combined organic layer was washed with saturated brine and dried over sodium sulfate. The solvent was evaporated and the obtained residue was purified by silica-gel column chromatography (hexane:ethyl acetate=l:l) to give tert-butyl[2-(3,4-dichlorobenzylamino)-1,1-dimethylethyl]carbamate (290 mg).

Workup

  1. customremoved from an ice-bath
  2. additionA borane-tetrahydrofuran complex (1.0 M/tetrahydrofuran solution) (5 ml) was added every 30 minutes twice in total
  3. customTo the obtained reaction mixture
  4. temperaturecooling
  5. customthe solvent was evaporated
  6. dissolutionThe obtained residue was dissolved in tetrahydrofuran (10 ml)
  7. stirring1N aqueous sodium hydroxide solution (4 ml) and the mixture was stirred at 90° C. for 1 hr
  8. customThe obtained reaction mixture
  9. extractionwas extracted twice with toluene
  10. washthe combined organic layer was washed with saturated brine
  11. dry with materialdried over sodium sulfate
  12. customThe solvent was evaporated
  13. customthe obtained residue was purified by silica-gel column chromatography (hexane:ethyl acetate=l:l)

Sources & evidence

ORD record
ord-27b7586d87884cc28edb2adc78273223
Source dataset
uspto-grants-2007_05
Patent number
US07211572B2

Reaction notes

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