m-Toluidine → 1292285-22-3

HRID 1748932Notes

Reaction equation

HRID 1748932 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

Procedure

In a 200 mL three-neck flask were put 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 the mixture was set to 80° C., followed by stirring for 2.0 hours. After the stirring, 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. 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) and recrystallized with a mixed solvent of toluene and hexane. Accordingly, 2.8 g of the target substance, white solid, was obtained in 82% yield. The synthesis scheme of this Step 1 is shown in (J-1).

Workup

  1. customIn a 200 mL three-neck flask were put
  2. customwas set to 60° C.
  3. customwas set to 80° C.
  4. filtrationAfter the stirring, 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
  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. customrecrystallized with a mixed solvent of toluene and hexane
  10. customAccordingly, 2.8 g of the target substance, white solid, was obtained in 82% yield
  11. customThe synthesis scheme of this Step 1

Sources & evidence

ORD record
ord-3c89e28ac8bc4ccd8275346be9be866d
Source dataset
uspto-grants-2015_10
Patent number
US09153627B2

Reaction notes

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