3-tert-Butyltoluene → 1-(Bromomethyl)-3-tert-butylbenzene

HRID 911272

Reaction equation

HRID 911272 reaction equation
[C:1]([C:5]1[CH:6]=[C:7]([CH3:11])[CH:8]=[CH:9][CH:10]=1)([CH3:4])([CH3:3])[CH3:2].C1C(=O)N([Br:19])C(=O)C1>C(Cl)(Cl)(Cl)Cl>[Br:19][CH2:11][C:7]1[CH:8]=[CH:9][CH:10]=[C:5]([C:1]([CH3:4])([CH3:3])[CH3:2])[CH:6]=1

Participants

4

Reactant 2

HCID 337113-tert-ButyltolueneHCID 67184N-bromobutanimide

Product 1

HCID 140976451-(Bromomethyl)-3-tert-butylbenzene

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

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. temperaturewith simultaneous heating
  2. temperatureto reflux for 1 h
  3. filtrationfilter
  4. concentrationconcentrate filtrate to dryness

Sources & evidence

ORD record
ord-44c10ecfc9224be68978ee7c1db9d603
Source dataset
uspto-grants-2011_09
Patent number
US08022062B2

Linked notes

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