4-Chloroaniline → HCID 21982721, compound

HRID 11009Notes

Reaction equation

HRID 11009 reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=3)[C:5]([CH3:16])([CH3:15])[C:4]=2[CH:3]=1.[Cl:17][C:18]1[CH:24]=[CH:23][C:21]([NH2:22])=[CH:20][CH:19]=1.CC(C)([O-])C.[Na+].C1(P(C2C=CC=CC=2)C2C=CC3C(=CC=CC=3)C=2C2C3C(=CC=CC=3)C=CC=2P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd].[Pd].CCCCCC.O1CCOCC1>[Cl:17][C:18]1[CH:24]=[CH:23][C:21]([NH:22][C:2]2[CH:14]=[CH:13][C:12]3[C:11]4[C:6](=[CH:7][CH:8]=[CH:9][CH:10]=4)[C:5]([CH3:16])([CH3:15])[C:4]=3[CH:3]=2)=[CH:20][CH:19]=1

Participants

8

Reactant 4

HCID 78124-ChloroanilineHCID 634876Binap, (A+-)-HCID 109456062-Bromo-9,9-dimethylfluoreneHCID 23676156Sodium t-butoxide

Product 1

HCID 21982721HCID 21982721, compound

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 8058HexaneSolventHCID 312751,4-DioxaneSolvent

Conditions

Temperature
80 °C

Procedure

A 500 ml, 5-neck reaction flask was charged with 2-bromo-9,9-dimethyl-9H-fluorene (25.0 g) (as prepared above), 4-chloroaniline (12.9 g), sodium tert-butoxide (12.3 g), rac-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (rac-BINAP) (0.4 g), tris(dibenzylideneacetone)-dipalladium(0) (Pd2(dba)3) (0.2 g) and 1,4-dioxane (180 ml). This mixture was heated with stirring to 80° C. and held at this temperature for 66 hours, after which time the reaction was deemed complete as indicated by TLC analysis. The reaction mixture was allowed to cool to room temperature and then poured into a beaker containing hexane (1 litre). Residual solids were removed by filtration and the filter cake washed with hexane (300 ml). The combined organic filtrate and washings were concentrated to yield a black/brown oil which was purified by dry flash column chromatography. The title amine was isolated as a red/brown viscous oil. (12.8 g). iii) Preparation of N,N-bis(4-chlorophenyl)-(9,9-dimethyl-9H-fluoren-2-yl)-amine

Workup

  1. customA 500 ml, 5-neck reaction flask
  2. temperatureThis mixture was heated
  3. temperatureto cool to room temperature
  4. additionpoured into a beaker
  5. customResidual solids were removed by filtration
  6. washthe filter cake washed with hexane (300 ml)
  7. concentrationThe combined organic filtrate and washings were concentrated
  8. customto yield a black/brown oil which
  9. customwas purified
  10. customby dry flash column chromatography

Sources & evidence

ORD record
ord-befb3972b18f4d6196654710f6ab3286
Source dataset
uspto-grants-2006_08
Patent number
US07095044B2

Reaction notes

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