Methyl iodide → Benzyl 3-bromo-5-cyanophenyl(methyl)carbamate

HRID 2070958Notes

Reaction equation

HRID 2070958 reaction equation
[Br:1][C:2]1[CH:3]=[C:4]([NH:10][C:11](=[O:20])[O:12][CH2:13][C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)[CH:5]=[C:6]([C:8]#[N:9])[CH:7]=1.[H-].[Na+].[CH3:23]I>C1COCC1>[Br:1][C:2]1[CH:3]=[C:4]([N:10]([CH3:23])[C:11](=[O:20])[O:12][CH2:13][C:14]2[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=2)[CH:5]=[C:6]([C:8]#[N:9])[CH:7]=1

Participants

5

Reactant 3

HCID 6328Methyl iodideHCID 24758Sodium hydrideHCID 68671401benzyl N-(3-bromo-5-cyanophenyl)carbamate

Product 1

HCID 68671106Benzyl 3-bromo-5-cyanophenyl(methyl)carbamateYield 24.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

To a stirring solution of 773 mg (2.33 mmol) of benzyl 3-bromo-5-cyanophenylcarbamate in 10 mL of THF at 0° C. was added 231 mg of NaH (60% dispersion in mineral oil). After 1 h, 300 μL (4.82 mmol) of methyl iodide was added, the ice bath was removed, and the red mixture was stirred at r.t. with the light off. After 17 h, saturated NH4Cl, H2O, and EtOAc were added and the layers separated. The organic layer was washed with brine, dried over Na2SO4, filtered, and concentrated. Purification by flash silica gel chromatography (5% EtOAc/hexanes) provided 195 mg of benzyl 3-bromo-5-cyanophenyl(methyl)carbamate in 24% yield.

Workup

  1. customthe ice bath was removed
  2. waitAfter 17 h
  3. additionsaturated NH4Cl, H2O, and EtOAc were added
  4. customthe layers separated
  5. washThe organic layer was washed with brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated
  9. customPurification by flash silica gel chromatography (5% EtOAc/hexanes)

Sources & evidence

ORD record
ord-abc508fc16a946feba9062cd6f7f8b72
Source dataset
uspto-grants-2012_10
Patent number
US08299267B2

Reaction notes

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