3,5-Dimethylaniline → HCID 67105832, compound

HRID 239204Notes

Reaction equation

HRID 239204 reaction equation
Br[C:2]1[CH:7]=[CH:6][C:5]([C:8]2([C:21]3[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=3)[C:20]3[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=3[C:14]3[C:9]2=[CH:10][CH:11]=[CH:12][CH:13]=3)=[CH:4][CH:3]=1.CC(C)([O-])C.[Na+].[CH3:33][C:34]1[CH:35]=[C:36]([CH:38]=[C:39]([CH3:41])[CH:40]=1)[NH2:37].C(P(C(C)(C)C)C(C)(C)C)(C)(C)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.[Pd].CCCCCC.C1(C)C=CC=CC=1>[CH3:33][C:34]1[CH:35]=[C:36]([NH:37][C:2]2[CH:7]=[CH:6][C:5]([C:8]3([C:21]4[CH:26]=[CH:25][CH:24]=[CH:23][CH:22]=4)[C:20]4[CH:19]=[CH:18][CH:17]=[CH:16][C:15]=4[C:14]4[C:9]3=[CH:10][CH:11]=[CH:12][CH:13]=4)=[CH:4][CH:3]=2)[CH:38]=[C:39]([CH3:41])[CH:40]=1

Participants

8

Reactant 4

HCID 79493,5-DimethylanilineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 577463459-(4-Bromophenyl)-9-phenylfluorene

Product 1

HCID 67105832HCID 67105832, compoundYield 92.9%

Reagents, catalysts & solvents 3

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalystHCID 1140TolueneSolventHCID 8058HexaneSolvent

Conditions

Temperature
80 °C

Procedure

In a 200 mL three-neck flask were put 3.6 g (9.1 mmol) of 9-(4-bromophenyl)-9-phenylfluorene and 2.7 g (27.7 mmol) of sodium tert-butoxide. The air in the flask was replaced with nitrogen. To this mixture were added 46.0 mL of toluene and 1.2 mL (9.6 mmol) of 3,5-dimethylaniline. The temperature of this mixture was set to 60° C., and 53.2 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0) was added to the mixture. The temperature of the mixture was raised to 80° C., followed by stirring for 0.5 hours. Then, 0.30 mL of a 10% hexane solution of tri(tert-butyl)phosphine was added to the mixture, which was then stirred for 4.5 hours. After the stirring, the mixture was suction-filtered through Florisil, Celite, and alumina to give a filtrate. The filtrate was concentrated to give a solid, which was then purified by silica gel column chromatography (the developing solvent has a 1:1 ratio of hexane to toluene) to give a while solid. Recrystallization of the obtained white solid from toluene and hexane gave 3.7 g of a white solid in 92% yield, which was the substance to be produced. The synthesis scheme of this Step 1 is shown in the following (E9-1).

Workup

  1. customIn a 200 mL three-neck flask were put
  2. customwas set to 60° C.
  3. stirringwas then stirred for 4.5 hours
  4. filtrationAfter the stirring, the mixture was suction-filtered through Florisil, Celite, and alumina
  5. customto give a filtrate
  6. concentrationThe filtrate was concentrated
  7. customto give a solid, which
  8. customwas then purified by silica gel column chromatography (the developing solvent
  9. customto give a while solid
  10. customRecrystallization of the obtained white solid from toluene and hexane

Sources & evidence

ORD record
ord-a09bf8f6470049759a94104a2272054e
Source dataset
uspto-grants-2014_02
Patent number
US08642190B2

Reaction notes

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