Water → 1-(Azidomethyl)-3-tert-butylbenzene

HRID 911273

Reaction equation

HRID 911273 reaction equation
Br[CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])[CH:4]=1.[N-:13]=[N+:14]=[N-:15].[Na+].O>CN(C=O)C>[N:13]([CH2:2][C:3]1[CH:8]=[CH:7][CH:6]=[C:5]([C:9]([CH3:12])([CH3:11])[CH3:10])[CH:4]=1)=[N+:14]=[N-:15]

Participants

5

Reactant 3

HCID 962WaterHCID 33557Sodium AzideHCID 140976451-(Bromomethyl)-3-tert-butylbenzene

Product 1

HCID 866295991-(Azidomethyl)-3-tert-butylbenzene

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

Dissolve 3-tert-butyltoluene (0.5 mL, 2.9 mmol) in carbon tetrachloride (20 mL). Add NBS (530 mg, 3 mmol) and irradiate the reaction mixture with a 250 watt sun-lamp with simultaneous heating to reflux for 1 h. Cool to ambient temperature, filter, and concentrate filtrate to dryness to give crude 1-bromomethyl-3-tert-butylbenzene. Dissolve crude 1-bromomethyl-3-tert-butylbenzene (600 mg) in anhydrous DMF. Add portion wise sodium azide (260 mg, 4 mmol) and stir at room temperature for 2 h. Pour the mixture into water (250 mL), extract with EtOAc (3×50 mL), wash combined organic extracts with brine, dry over MgSO4, filter and evaporate solvent to give crude 1-azidomethyl-3-tert-butylbenzene, that was used without further purification. Dissolve crude 1-azidomethyl-3-tert-butylbenzene in methanol containing 10% Pd/C (75 mg) at 5° C., and stir the resulting slurry under 1 atm H2 for 1 h. Filtrate, concentrate in vacuo and purify by chromatography on silica gel eluting sequentially with hexane/EtOAc (4:1 and 1:1), EtOAc, methanol and 2M ammonia in methanol to give the title compound (255 mg, 53% overall). MS (ES+) m/z: 164 (M+H)+.

Workup

  1. extractionextract with EtOAc (3×50 mL)
  2. washwash
  3. dry with materialdry over MgSO4
  4. filtrationfilter
  5. customevaporate solvent

Sources & evidence

ORD record
ord-e9bec9e92aae4a61996cd699359895a5
Source dataset
uspto-grants-2011_09
Patent number
US08022062B2

Linked notes

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