Diphenylamine → 4-Bromodiphenylamine

HRID 2068447Notes

Reaction equation

HRID 2068447 reaction equation
[C:1]1([NH:7][C:8]2[CH:13]=[CH:12][CH:11]=[CH:10][CH:9]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Br-:14].[Br-].[Br-].C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.C([N+](CCCC)(CCCC)CCCC)CCC.C(Cl)(Cl)Cl.C1(NC2C=CC=CC=2)C=CC=CC=1>C(Cl)(Cl)Cl>[CH:11]1[CH:10]=[CH:9][C:8]([NH:7][C:1]2[CH:2]=[CH:3][C:4]([Br:14])=[CH:5][CH:6]=2)=[CH:13][CH:12]=1

Participants

5

Reactant 3

HCID 11487DiphenylamineHCID 23500184Tetra-n-butylammonium tribromideHCID 68426310HCID 68426310, compound2×

Product 1

HCID 64257864-Bromodiphenylamine

Reagents, catalysts & solvents 1

HCID 6212ChloroformSolvent2×

Procedure

In a 1000-mL Erlenmeyer flask were placed 20 g (118.1 mmol) of diphenylamine, 500 mL of chloroform, and an ellipsoidal stirring chip. In a 500-mL beaker was placed 113.8 g (236.2 mmol) of tetrabutylammoniumtribromide (TBABr3), which was dissolved in 200 mL of chloroform added later. The resulting solution was added dropwise to the chloroform-diphenylamine solution, and the mixture was stirred for 20 hours at room temperature in the air. Then, the chloroform-diphenylamine solution was transferred to a 1000-mL separatory funnel and washed seven times with 100 mL of saturated aqueous solution of sodium thiosulfate. The organic layer was transferred to a 1000-mL Erlenmeyer flask and then dehydrated with 100 g of anhydrous magnesium sulfate. With the anhydrous magnesium sulfate removed by filtration, the chloroform solution was transferred to a 1000-mL eggplant-shaped flask and freed of chloroform by means of an evaporator. The resulting crude product was purified by means of a silica gel column (hexane:chloroform=1:1) (Yields: 70%).

Workup

  1. additionadded later
  2. washwashed seven times with 100 mL of saturated aqueous solution of sodium thiosulfate
  3. customWith the anhydrous magnesium sulfate removed by filtration
  4. customthe chloroform solution was transferred to a 1000-mL eggplant-shaped flask
  5. customfreed of chloroform by means of an evaporator
  6. customThe resulting crude product was purified by means of a silica gel column (hexane:chloroform=1:1) (Yields: 70%)

Sources & evidence

ORD record
ord-cf4c9fc938b840b0ae693e8527c2bca0
Source dataset
uspto-grants-2012_10
Patent number
US08298444B2

Reaction notes

Loading…