Diphenylamine → 9,9-Dimethoxyethyl-2-diphenylaminofluorene

HRID 720020Notes

Reaction equation

HRID 720020 reaction equation
BrCC[C:4]1[C:16]2[C:15]([O:19][CH3:20])([O:17][CH3:18])[C:14]3[C:9](=[CH:10][CH:11]=[CH:12][CH:13]=3)[C:8]=2[CH:7]=[CH:6][CH:5]=1.[C:21]1([NH:27][C:28]2[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=2)[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=1.[CH:34]1C=CC(P(C2C(C3C(P(C4C=CC=CC=4)C4C=CC=CC=4)=CC=C4C=3C=CC=C4)=C3C(C=CC=C3)=CC=2)C2C=CC=CC=2)=C[CH:39]=1.CC(C)([O-])C.[Na+]>C1(C)C=CC=CC=1.C(OCC)C.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]>[CH3:20][O:19][C:15]1([O:17][CH3:18])[C:14]2[C:9]([CH2:34][CH3:39])=[C:10]([N:27]([C:21]3[CH:22]=[CH:23][CH:24]=[CH:25][CH:26]=3)[C:28]3[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=3)[CH:11]=[CH:12][C:13]=2[C:4]2[C:16]1=[CH:8][CH:7]=[CH:6][CH:5]=2

Participants

8

Reactant 4

HCID 11487DiphenylamineHCID 634876Binap, (A+-)-HCID 23676156Sodium t-butoxideHCID 695870882-Bromo-9,9-dimethoxyethylfluorene

Product 1

HCID 695867379,9-Dimethoxyethyl-2-diphenylaminofluoreneYield 506.1%

Reagents, catalysts & solvents 3

HCID 9811564Bis(dibenzylideneacetone)palladiumCatalystHCID 1140TolueneSolventHCID 3283Diethyl EtherSolvent

Procedure

In a round-bottom flask, a mixture of 2-bromo-9,9-dimethoxyethylfluorene (2.0 g, 5.54 mmol), diphenylamine (1.12 g, 6.65 mmol), tris(dibenzylideneacetone)dipalladium (0) (0.012 g, 0.25 mmol %), rac-BINAP (0.025 g, 0.75 mmol %), and sodium t-butoxide (0.74 g, 7.76 mmol) in dry toluene (100 ml ) was placed and heated at the refluxing temperature of the solvent for 16 h under an atmospheric pressure of nitrogen. After cooling the reaction mixture to room temperature, it was diluted with diethylether (60 ml), washed with brine (40 ml) and water. Organic layer was dried over sodium sulfate and concentrated in vacuuo. The crude product was purified by preparative thin layer chromatography (silica gel, Rf=0.3 using hexane-EtOAc-toluene/1:1:3 as eluent) to give 9,9-dimethoxyethyl-2-diphenylaminofluorene (1.6 g).

Workup

  1. temperatureheated at the refluxing temperature of the solvent for 16 h under an atmospheric pressure of nitrogen
  2. washwashed with brine (40 ml) and water
  3. dry with materialOrganic layer was dried over sodium sulfate
  4. concentrationconcentrated in vacuuo
  5. customThe crude product was purified by preparative thin layer chromatography (silica gel, Rf=0.3 using hexane-EtOAc-toluene/1:1:3 as eluent)

Sources & evidence

ORD record
ord-474c5d125f364a8f8a9866a0b557d2f8
Source dataset
uspto-grants-2006_11
Patent number
US07132572B2

Reaction notes

Loading…