Hydrochloric Acid → n-Ethyl n-(2-benzyloxy-5-bromobenzyl)amine hydrochloride salt

HRID 1870768Notes

Reaction equation

HRID 1870768 reaction equation
[CH2:1](Br)[C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1.[Br:9][C:10]1[CH:11]=[CH:12][C:13]([OH:18])=[C:14]([CH:17]=1)[CH:15]=O.C([O-])([O-])=O.[K+].[K+].[ClH:25].[CH2:26]([NH2:28])[CH3:27].[BH4-].[Na+].Cl>CN1CCCC1=O.CO.C(OCC)(=O)C>[ClH:25].[CH2:26]([NH:28][CH2:15][C:14]1[CH:17]=[C:10]([Br:9])[CH:11]=[CH:12][C:13]=1[O:18][CH2:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][CH:3]=1)[CH3:27]

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 7498Benzyl BromideHCID 11198Ethylamine hydrochlorideHCID 11430Potassium CarbonateHCID 728635-BromosalicylaldehydeHCID 4311764Sodium borohydride

Product 1

HCID 17290784n-Ethyl n-(2-benzyloxy-5-bromobenzyl)amine hydrochloride saltYield 76.7%

Reagents, catalysts & solvents 3

HCID 887MethanolSolventHCID 8857Ethyl AcetateSolventHCID 13387N-methyl-2-pyrrolidoneSolvent2×

Conditions

Temperature
37.5 °C

Procedure

Benzyl bromide (71.4 ml) was added dropwise to a mixture of 5-bromo-2-hydroxybenzaldehyde (100.5 g) and K2CO3 (207.5 g) in 1-methyl-2-pyrrolidinone (500 ml) at 30° C. over 1 hour. The mixture was stirred for 3 hours at 35-40° C. A solution of ethylamine hydrochloride (57.1 g) in methanol (250 ml) was added over 30 minutes at 35° C. and the mixture stirred for 3 hours at 35-40° C. A solution of sodium borohydride (26.5 g) in 1-methyl-2-pyrrolidinone (300 ml) was added over 2 hours at 35-40° C. and the mixture stirred at 40-45° C. for 2 hours. The mixture was cooled (10° C.), diluted with ethyl acetate (200 ml) and acidified with 2N HCl (3,500 ml). The resulting precipitate was filtered off, washed with toluene and 40-60 petroleum ether and dried under vacuum at 60° C. The residue was purified by stirring in a mixture of acetonitrile (140 ml) and toluene (700 ml) at 80° C. for 30 minutes, cooling to 10° C. and filtering off the product to give N-ethyl N-(2-benzyloxy-5-bromobenzyl)amine hydrochloride salt (13.6 g, 76.7% yield).

Workup

  1. stirringthe mixture stirred for 3 hours at 35-40° C
  2. stirringthe mixture stirred at 40-45° C. for 2 hours
  3. temperatureThe mixture was cooled (10° C.)
  4. filtrationThe resulting precipitate was filtered off
  5. washwashed with toluene and 40-60 petroleum ether
  6. customdried under vacuum at 60° C
  7. customThe residue was purified
  8. stirringby stirring in a mixture of acetonitrile (140 ml) and toluene (700 ml) at 80° C. for 30 minutes
  9. temperaturecooling to 10° C.
  10. filtrationfiltering off the product

Sources & evidence

ORD record
ord-3385ccb12a5c42a7a82e91816b6c36b5
Source dataset
uspto-grants-2000_08
Patent number
US06100258

Reaction notes

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