4-Bromo-2,6-xylidine → N-(4-Bromo-2,6-dimethylphenyl)(4,5-dimethyl-6H-cyclopenta[b]thien-6-yl) dimethylsilanamine

HRID 1922327Notes

Reaction equation

HRID 1922327 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([CH3:9])[C:5]([NH2:6])=[C:4]([CH3:10])[CH:3]=1.[Li]CCCC.Cl[Si:17]([CH:20]1[C:24]2[S:25][CH:26]=[CH:27][C:23]=2[C:22]([CH3:28])=[C:21]1[CH3:29])([CH3:19])[CH3:18]>C1COCC1>[Br:1][C:2]1[CH:8]=[C:7]([CH3:9])[C:5]([NH:6][Si:17]([CH:20]2[C:24]3[S:25][CH:26]=[CH:27][C:23]=3[C:22]([CH3:28])=[C:21]2[CH3:29])([CH3:18])[CH3:19])=[C:4]([CH3:10])[CH:3]=1

Participants

5

Reactant 3

HCID 905494-Bromo-2,6-xylidineHCID 58526148Chloro(4,5-dimethyl-6H-cyclopenta[b]thien-6-yl)dimethylsilaneHCID 178418339Butyllithium

Product 1

HCID 58526147N-(4-Bromo-2,6-dimethylphenyl)(4,5-dimethyl-6H-cyclopenta[b]thien-6-yl) dimethylsilanamine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Under an argon atmosphere, to a solution of 12.4 g (61.9 mmol) of 4-bromo-2,6-dimethylaniline in 300 ml of THF, 16.5 ml of 2.5 M (41.2 mmol) nBuLi in hexanes was added at −80° C. This mixture was warmed for ca. 2 hour to ambient temperature. Then, the resulting solution was added dropwise over ca. 1 hour, while vigorously stirring, to a solution of 10.0 g (41.2 mmol) of chloro(4,5-dimethyl-6H-cyclopenta[b]thien-6-yl)dimethylsilane in 50 ml of THF. The resulting mixture was stirred overnight at ambient temperature, and then, evaporated to dryness. To the residue, 150 ml of toluene was added. This mixture was filtered through a glass frit (G4). The filtrate was evaporated to dryness. Fractional distillation gave a yellow liquid, bp 154-156° C./0.05 mm Hg. The product crystallizes slowly at ambient temperature. Yield 8.36 g (50%).

Workup

  1. temperatureThis mixture was warmed for ca. 2 hour to ambient temperature
  2. additionThen, the resulting solution was added dropwise over ca. 1 hour
  3. customevaporated to dryness
  4. additionTo the residue, 150 ml of toluene was added
  5. filtrationThis mixture was filtered through a glass frit (G4)
  6. customThe filtrate was evaporated to dryness
  7. distillationFractional distillation
  8. customgave a yellow liquid, bp 154-156° C./0.05 mm Hg
  9. customThe product crystallizes slowly at ambient temperature

Sources & evidence

ORD record
ord-ca0df73610674f659fde1aa65bc9eeee
Source dataset
uspto-grants-2012_05
Patent number
US08173828B2

Reaction notes

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