Bromoacetyl bromide → 7-Bromoacetyl-9,9-diethyl-2-diphenylaminofluorene

HRID 720017Notes

Reaction equation

HRID 720017 reaction equation
[Cl-].[Al+3].[Cl-].[Cl-].[C:5]1([N:11]([C:29]2[CH:34]=[CH:33][CH:32]=[CH:31][CH:30]=2)[C:12]2[CH:24]=[CH:23][C:22]3[C:21]4[C:16](=[CH:17][CH:18]=[CH:19][CH:20]=4)[C:15]([CH2:27][CH3:28])([CH2:25][CH3:26])[C:14]=3[CH:13]=2)[CH:10]=[CH:9][CH:8]=[CH:7][CH:6]=1.[Br:35][CH2:36][C:37](Br)=[O:38]>ClCCCl>[Br:35][CH2:36][C:37]([C:18]1[CH:17]=[C:16]2[C:21]([C:22]3[CH:23]=[CH:24][C:12]([N:11]([C:5]4[CH:6]=[CH:7][CH:8]=[CH:9][CH:10]=4)[C:29]4[CH:30]=[CH:31][CH:32]=[CH:33][CH:34]=4)=[CH:13][C:14]=3[C:15]2([CH2:27][CH3:28])[CH2:25][CH3:26])=[CH:20][CH:19]=1)=[O:38]

Participants

5

Reactant 3

HCID 61147Bromoacetyl bromideHCID 6451240Aluminum(III) ChlorideHCID 219021849,9-Diethyl-2-diphenylaminofluorene

Product 1

HCID 219021827-Bromoacetyl-9,9-diethyl-2-diphenylaminofluoreneYield 66.3%

Reagents, catalysts & solvents 1

HCID 111,2-DichloroethaneSolvent2×

Procedure

To a suspension of aluminium chloride (0.375 g, 2.82 mmol) in 1,2-dichloroethane (15 ml) at 0° C. was added a solution of 2-diphenylamino-9,9-diethylfluorene (1.0 g, 2.57 mmol) in 1,2-dichloroethane (15 ml). Bromoacetyl bromide (0.269 ml, 3.08 mmol) was added over a period of 10 min to maintain a steady reaction temperature between 0–10° C. under an ice-bath. At the end of addition, the mixture was warmed to ambient temperature, stirred for another 4 h, and quenched by a slow addition of water (50 ml) to maintain the mixture temperature below 45° C. Organic layer was washed subsequently with dil. HCl (1.0 N, 50 ml) and water (50 ml, twice). It was concentrated in vacuuo to give crystalline yellow solids. These crude products were purified by column chromatography (silica gel, hexane-toluene/3:2 as eluent, Rf=0.3 on thin layer chromatography using the same solvent mixture as eluent) to afford 7-bromoacetyl-9,9-diethyl-2-diphenylaminofluorene (0.87 g) as yellow crystalline solids in a yield of 66%

Workup

  1. temperatureto maintain a steady reaction temperature between 0–10° C. under an ice-bath
  2. additionAt the end of addition
  3. customquenched by a slow addition of water (50 ml)
  4. temperatureto maintain the mixture temperature below 45° C
  5. washOrganic layer was washed subsequently with dil. HCl (1.0 N, 50 ml) and water (50 ml
  6. concentrationIt was concentrated in vacuuo
  7. customto give crystalline yellow solids
  8. customThese crude products were purified by column chromatography (silica gel, hexane-toluene/3:2 as eluent

Sources & evidence

ORD record
ord-e691b07cf0f64d4dbd59149634668713
Source dataset
uspto-grants-2006_11
Patent number
US07132572B2

Reaction notes

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