Water → 2-(4-Bromo-2,6-dimethyl-phenyl)-1,1,1,3,3,3-hexamethyl-disilazane

HRID 1917051Notes

Reaction equation

HRID 1917051 reaction equation
[Br:1][C:2]1[CH:8]=[C:7]([CH3:9])[C:5]([NH2:6])=[C:4]([CH3:10])[CH:3]=1.C([Li])CCC.[CH3:16][Si:17](Cl)([CH3:19])[CH3:18].O>O1CCCC1>[Br:1][C:2]1[CH:8]=[C:7]([CH3:9])[C:5]([N:6]([Si:17]([CH3:19])([CH3:18])[CH3:16])[Si:17]([CH3:19])([CH3:18])[CH3:16])=[C:4]([CH3:10])[CH:3]=1

Participants

6

Reactant 4

HCID 962WaterHCID 6397Chlorotrimethylsilane2×HCID 905494-Bromo-2,6-xylidineHCID 178418339Butyllithium2×

Product 1

HCID 594978222-(4-Bromo-2,6-dimethyl-phenyl)-1,1,1,3,3,3-hexamethyl-disilazane

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Conditions

Temperature
-78 °C

Procedure

To a solution of 4-bromo-2,6-dimethylaniline (commercially available) (40 g, 0.2 mol) in tetrahydrofuran (500 ml) under a nitrogen atmosphere was added a solution of n-butyl lithium in hexanes (1.6 M) (125 ml, 0.2 mol). During this operation, the internal temperature was kept between −70° C. and −78° C. After five minutes, trimethylsilyl chloride (25 ml, 0.2 mol) was added whilst the internal temperature was kept below −68° C. After five minutes, the cooling bath was replaced with a water bath and the internal temperature rose to 0° C. Then the cooling bath was put back and the reaction mixture was cooled to −78° C. To this solution, a solution of n-butyl lithium in hexanes (1.6 M) (125 ml, 0.2 mol) was added whilst keeping the internal temperature below −70° C., followed by addition of trimethylsilyl chloride (30 ml, 0.237 mol) whilst keeping the internal temperature below −68° C. The reaction mixture was gradually allowed to warm to 20° C. Hexanes (200 ml) and water (40 ml) were added and the phases were separated. The organic phase was washed with brine, dried over sodium sulfate, and concentrated. The residue was distilled under a high vacuum leading to the title compound as a colorless oil which crystallized on standing. M.p. 47-52° C. 1H-NMR (CDCl3, 400 MHz): 0.08 (s, 18H), 2.21 (s, 6H), 7.15 (s, 2H) ppm.

Workup

  1. customwas kept between −70° C. and −78° C
  2. customwas kept below −68° C
  3. waitAfter five minutes
  4. customthe cooling bath was replaced with a water bath
  5. customrose to 0° C
  6. customthe internal temperature below −70° C.
  7. customthe internal temperature below −68° C
  8. temperatureto warm to 20° C
  9. customthe phases were separated
  10. washThe organic phase was washed with brine
  11. dry with materialdried over sodium sulfate
  12. concentrationconcentrated
  13. distillationThe residue was distilled under a high vacuum
  14. customcrystallized

Sources & evidence

ORD record
ord-e584e1e21a8c45b8a37fb9430fe3fe7a
Source dataset
uspto-grants-2013_12
Patent number
US08618173B2

Reaction notes

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