Methylamine → 2-(4-Tert-butylphenyl)ethan-1-amine

HRID 1356830Notes

Reaction equation

HRID 1356830 reaction equation
C(=O)([O-])[O-].[Na+].[Na+].[CH3:7][NH2:8].[C:9]([C:13]1[CH:20]=[CH:19][C:16]([CH2:17]Br)=[CH:15][CH:14]=1)([CH3:12])([CH3:11])[CH3:10]>CO>[C:9]([C:13]1[CH:20]=[CH:19][C:16]([CH2:17][CH2:7][NH2:8])=[CH:15][CH:14]=1)([CH3:12])([CH3:11])[CH3:10]

Participants

5

Reactant 3

HCID 6329MethylamineHCID 10340Sodium CarbonateHCID 878361-(Bromomethyl)-4-(1,1-dimethylethyl)benzene

Product 1

HCID 27356892-(4-Tert-butylphenyl)ethan-1-amineYield 53.7%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent2×

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. additiona mixture of the target compound
  2. temperatureWhile the mixture was cooled in an ice bath
  3. customThe mixture was removed from the ice bath
  4. customMethanol was removed under reduced pressure
  5. extractionfollowed by extraction with ether (400 ml)
  6. extractionThe ether layer was extracted with 1N hydrochloric acid twice (200 ml and 100 ml)
  7. extractionthe aqueous layer was extracted with ethyl acetate
  8. extractionextracted with ether (400 ml)
  9. dry with materialby drying over magnesium sulfate
  10. customThe solvent was evaporated under reduced pressure
  11. customthe residue was purified by silica gel column chromatography (chloroform:methanol=200:1→100:1→20:1)

Sources & evidence

ORD record
ord-7c6a6cc2708443878ab3b581742c5f02
Source dataset
uspto-grants-2003_07
Patent number
US06586633B1

Reaction notes

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