4-tert-Butyltoluene → 1-(Bromomethyl)-4-(1,1-dimethylethyl)benzene

HRID 1356829Notes

Reaction equation

HRID 1356829 reaction equation
[C:1]([C:5]1[CH:10]=[CH:9][C:8]([CH3:11])=[CH:7][CH:6]=1)([CH3:4])([CH3:3])[CH3:2].[Br:12]N1C(=O)CCC1=O>C(Cl)(Cl)(Cl)Cl.C(OOC(=O)C1C=CC=CC=1)(=O)C1C=CC=CC=1>[C:1]([C:5]1[CH:6]=[CH:7][C:8]([CH2:11][Br:12])=[CH:9][CH:10]=1)([CH3:4])([CH3:3])[CH3:2]

Participants

5

Reactant 2

HCID 73904-tert-ButyltolueneHCID 67184N-bromobutanimide

Product 1

HCID 878361-(Bromomethyl)-4-(1,1-dimethylethyl)benzeneYield 100%

Reagents, catalysts & solvents 2

HCID 7187Benzoyl PeroxideCatalystHCID 5943Carbon TetrachlorideSolvent

Procedure

p-tert-butyltoluene (14.8 g; 0.10 mol) was dissolved in carbon tetrachloride, and N-bromosuccinimide (17.8 g; 0.10 mol) and benzoyl peroxide (200 mg) were added thereto. The mixture was refluxed for 2 hours, and then cooled. Insoluble matter was filtered off, followed by washing with carbon tetrachloride. The filtrate was concentrated under reduced pressure, and the residue was dissolved in n-hexane, followed by drying over magnesium sulfate. The solvent was evaporated under reduced pressure, to thereby yield 22.7 g of p-tert-butylbenzyl bromide (yield: 100%). The thus-obtained product was analyzed by 1H-NMR, and was found to be a mixture of the target compound, starting compounds, and a dibromo compound (10:1:1). Sodium carbonate (10.6 g; 0.10 mol) was added to 40% solution of methylamine in methanol (200 ml). While the mixture was cooled in an ice bath, p-tert-butyl benzyl bromide (22.7 g; 0.10 mol) in methanol (20 ml) was added dropwise thereto. The mixture was removed from the ice bath, and stirred for 41 hours at room temperature. Methanol was removed under reduced pressure, and the residue was taken up in water, followed by extraction with ether (400 ml). The ether layer was extracted with 1N hydrochloric acid twice (200 ml and 100 ml), and the aqueous layer was extracted with ethyl acetate. The aqueous layer was alkalinized with aqueous 2N sodium hydroxide solution, and extracted with ether (400 ml), followed by drying over magnesium sulfate. The solvent was evaporated under reduced pressure, and the residue was purified by silica gel column chromatography (chloroform:methanol=200:1→100:1→20:1), to thereby yield 9.51 g of the target compound (yield: 53.7%).

Workup

  1. temperatureThe mixture was refluxed for 2 hours
  2. temperaturecooled
  3. filtrationInsoluble matter was filtered off
  4. washby washing with carbon tetrachloride
  5. concentrationThe filtrate was concentrated under reduced pressure
  6. dissolutionthe residue was dissolved in n-hexane
  7. dry with materialby drying over magnesium sulfate
  8. customThe solvent was evaporated under reduced pressure

Sources & evidence

ORD record
ord-aefa802dba304be7ad7e75300e0d6eda
Source dataset
uspto-grants-2003_07
Patent number
US06586633B1

Reaction notes

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