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

HRID 355686Notes

Reaction equation

HRID 355686 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-].[NH4+].[Br-:31].[Li+]>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:31])([O-:3])=[O:2]

Participants

6

Reactant 4

HCID 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 1

HCID 3283Diethyl EtherSolvent

Procedure

1.8 g (6.2 mmol) of 2-[(2,6-dinitrophenyl)amino]-benzyl alcohol was dissolved in a mixture of 50 ml of dictloromethane 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 methane-sulfonuyl 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. temperaturethe resulting mixture was heated
  7. temperatureunder reflux for 1 hour
  8. distillationAfter distilling off the solvent under reduced pressure
  9. customthe residue was purified by silica gel column chromatography

Sources & evidence

ORD record
ord-16ab1465f430442b918446398faccd01
Source dataset
uspto-grants-1998_11
Patent number
US05834462

Reaction notes

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