Chloride → 2((2,6-Dinitrophenyl)amino)benzyl bromide

HRID 1456938Notes

Reaction equation

HRID 1456938 reaction equation
[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[NH:13][C:14]1[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=1[CH2:16]O)([O-:3])=[O:2].C(N(CC)CC)C.[Cl-].[Cl-].[NH4+].[Br-:32].[Li+]>ClCCl.C(OCC)C>[N+:1]([C:4]1[CH:9]=[CH:8][CH:7]=[C:6]([N+:10]([O-:12])=[O:11])[C:5]=1[NH:13][C:14]1[CH:21]=[CH:20][CH:19]=[CH:18][C:15]=1[CH2:16][Br:32])([O-:3])=[O:2]

Participants

8

Reactant 5

HCID 312ChlorideHCID 8471TriethylamineHCID 25517Ammonium ChlorideHCID 82050Lithium BromideHCID 540886182-((2,6-Dinitrophenyl)amino)benzyl alcohol

Product 1

HCID 538353662((2,6-Dinitrophenyl)amino)benzyl bromideYield 22.9%

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

1.8 g (6.2 mmol) of 2-[(2,6-dinitrophenyl)amino]-benzyl alcohol was dissolved in a mixture of 50 ml of dichloromethane with 50 ml of ethyl ether. Under ice-cooling and stirring, 2.2 ml (15.5 mmol) of triethylamine and 0.58 ml (7.4 mmol) of methanesulfonuyl chloride were successively added thereto. After stirring for 30 minutes, the reaction mixture was poured into a saturated aqueous solution of ammonium chloride and extracted with ethyl acetate. After concentrating, the residue was dissolved in 150 ml of acetone. Then 2.7 g (31 mmol) of lithium bromide was. added and the resulting mixture was heated under reflux for 1 hour. After distilling off the solvent under reduced pressure, the residue was purified by silica gel column chromatography to thereby give 0.5 g of 2[(2,6-dinitrophenyl)amino]-benzyl bromide. This product was dissolved in 10 ml of dimethylformamide. After adding 216 mg (2.8 mmol) of thiourea, the mixture was stirred at room temperature for 5 hours. Then 10 ml of dimethylformamide, 157 mg (2.8 mmol) of potassium hydroxide and 2 ml of water were successively added thereto and the reaction mixture was heated at 100° C. for 3 hours. After cooling, the reaction mixture was poured into a saturated aqueous solution of sodium chloride and extracted with ethyl acetate. After concentrating, the residue was purified by silica gel. column chromatography. Thus 0.22 g of the title compound was obtained.

Workup

  1. temperatureUnder ice-cooling
  2. stirringAfter stirring for 30 minutes
  3. extractionextracted with ethyl acetate
  4. concentrationAfter concentrating
  5. dissolutionthe residue was dissolved in 150 ml of acetone
  6. additionadded
  7. temperaturethe resulting mixture was heated
  8. temperatureunder reflux for 1 hour
  9. distillationAfter distilling off the solvent under reduced pressure
  10. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-f030426479a146149139aea7079e8f5d
Source dataset
uspto-grants-1998_12
Patent number
US05846969

Reaction notes

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