m-Toluidine → 1292285-22-3

HRID 1189592Notes

Reaction equation

HRID 1189592 reaction equation
Br[C:2]1[CH:3]=[C:4]([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:5]=[CH:6][CH:7]=1.CC(C)([O-])C.[Na+].[NH2:33][C:34]1[CH:39]=[CH:38][CH:37]=[C:36]([CH3:40])[CH:35]=1.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>[CH3:40][C:36]1[CH:35]=[C:34]([NH:33][C:25]2[CH:24]=[CH:23][CH:22]=[C:21]([C:8]3([C:4]4[CH:5]=[CH:6][CH:7]=[CH:2][CH:3]=4)[C:9]4[CH:10]=[CH:11][CH:12]=[CH:13][C:14]=4[C:15]4[C:20]3=[CH:19][CH:18]=[CH:17][CH:16]=4)[CH:26]=2)[CH:39]=[CH:38][CH:37]=1

Participants

8

Reactant 4

HCID 7934m-ToluidineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 582335499-(3-Bromophenyl)-9-phenyl-9H-fluorene

Product 1

HCID 666917921292285-22-3Yield 82%

Reagents, catalysts & solvents 3

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

Conditions

Temperature
80 °C

Procedure

Into a 200 mL three-neck flask were placed 3.2 g (8.1 mmol) of 9-(3-bromophenyl)-9-phenylfluorene and 2.3 g (24.1 mmol) of sodium tert-butoxide. The air in the flask was replaced with nitrogen. To this mixture were added 40.0 mL of toluene, 0.9 mL (8.3 mmol) of m-toluidine, and 0.2 mL of a 10% hexane solution of tri(tert-butyl)phosphine. The temperature of this mixture was set to 60° C., and 44.5 mg (0.1 mmol) of bis(dibenzylideneacetone)palladium(0) was added to the mixture. The temperature of this mixture was raised to 80° C., and the mixture was stirred for 2.0 hours. After that, the mixture was suction-filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina to give a filtrate. A solid obtained by concentration of the obtained filtrate was purified by silica gel column chromatography (a developing solvent in which the ratio of hexane to toluene was 1:1) and recrystallized from a mixed solvent of toluene and hexane. Accordingly, 2.8 g of a white solid of the object of the synthesis was obtained in 82% yield. The synthesis scheme of Step 1 above is illustrated in the following scheme.

Workup

  1. customInto a 200 mL three-neck flask were placed
  2. customwas set to 60° C.
  3. filtrationAfter that, the mixture was suction-filtered through Florisil (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 540-00135), Celite (produced by Wako Pure Chemical Industries, Ltd., Catalog No. 531-16855), and alumina
  4. customto give a filtrate
  5. customA solid obtained by concentration of the obtained filtrate
  6. customwas purified by silica gel column chromatography (a developing solvent in which the ratio of hexane to toluene
  7. customrecrystallized from a mixed solvent of toluene and hexane

Sources & evidence

ORD record
ord-f07cb8d7c13f4377bab61deae5a397b4
Source dataset
uspto-grants-2014_03
Patent number
US08674114B2

Reaction notes

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