4-Bromo-N,N-bis(trimethylsilyl)aniline → HCID 58345210, compound

HRID 1888010Notes

Reaction equation

HRID 1888010 reaction equation
C([Li])CCC.Br[C:7]1[CH:21]=[CH:20][C:10]([N:11]([Si](C)(C)C)[Si](C)(C)C)=[CH:9][CH:8]=1.[CH3:22][C:23]([S:26]([N:28]=[C:29]1[CH2:32][O:31][CH2:30]1)=[O:27])([CH3:25])[CH3:24]>C1COCC1>[NH2:11][C:10]1[CH:20]=[CH:21][C:7]([C:29]2([NH:28][S:26]([C:23]([CH3:25])([CH3:24])[CH3:22])=[O:27])[CH2:32][O:31][CH2:30]2)=[CH:8][CH:9]=1

Participants

5

Reactant 3

HCID 40926204-Bromo-N,N-bis(trimethylsilyl)anilineHCID 468399952-Methyl-N-(oxetan-3-ylidene)propane-2-sulfinamideHCID 178418339Butyllithium

Product 1

HCID 58345210HCID 58345210, compoundYield 90%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
-78 °C

Procedure

A solution of n-butyllithium in hexanes (1.65 M, 5.14 mL) was added dropwise to a solution of 4-bromo-N,N-bis(trimethylsilyl)aniline (2.52 mL) in THF (14 mL) at −78° C. The resulting mixture was stirred for 1 h at −78° C. before a solution of 2-methyl-N-oxetan-3-ylidenepropane-2-sulfinamide in THF (2.8 mL) was added dropwise over the course of 15 minutes at −78° C. The reaction mixture was stirred for an additional 1 h at −78° C. then allowed to warm to room temperature. After being stirred for 18 h at room temperature, the reaction mixture was poured into ice cooled saturated sodium bicarbonate solution. The aqueous layer was extracted with ethyl acetate. The combined organic layer was washed with saturated sodium bicarbonate solution and brine and then dried over anhydrous sodium sulfate. The dried solution was filtered and the filtrate was concentrated to dryness. The residue was diluted with diisopropylether and extracted with 1 M citric acid solution. The aqueous extracts were combined and basified with sodium bicarbonate solid to pH>7. The basic aqueous layer was extracted with ethyl acetate and the organic layer was washed with brine. The organics were dried over anhydrous sodium sulfate and concentrated under reduced pressure. Purification by recrystallization with ethyl acetate and column chromatography (30-100% ethyl acetate in hexanes) gave the product (1.37 g, 90%). 400 M Hz 1H-NMR (DMSO-d6) δ: 7.07 (d, J=8.7 Hz, 2H), 5.56 (d, J=8.7 Hz, 2H), 6.05 (s, 1H), 5.10 (brs, 2H), 4.94 (dd, J=6.0 and 2.3 Hz, 2H), 4.83 (d, J=6.0 Hz, 1H), 4.60 (d, J=6.0 Hz, 1H), 1.08 (s, 9H).

Workup

  1. additionwas added dropwise over the course of 15 minutes at −78° C
  2. temperatureto warm to room temperature
  3. stirringAfter being stirred for 18 h at room temperature
  4. additionthe reaction mixture was poured into ice cooled saturated sodium bicarbonate solution
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. washThe combined organic layer was washed with saturated sodium bicarbonate solution and brine
  7. dry with materialdried over anhydrous sodium sulfate
  8. filtrationThe dried solution was filtered
  9. concentrationthe filtrate was concentrated to dryness
  10. additionThe residue was diluted with diisopropylether
  11. extractionextracted with 1 M citric acid solution
  12. extractionThe basic aqueous layer was extracted with ethyl acetate
  13. washthe organic layer was washed with brine
  14. dry with materialThe organics were dried over anhydrous sodium sulfate
  15. concentrationconcentrated under reduced pressure
  16. customPurification
  17. customby recrystallization with ethyl acetate and column chromatography (30-100% ethyl acetate in hexanes)

Sources & evidence

ORD record
ord-41cbe4b542a04a5280a1d5f32be00b7c
Source dataset
uspto-grants-2013_08
Patent number
US08501770B2

Reaction notes

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