Chloroselenobenzene → HCID 11012861, compound

HRID 1888299Notes

Reaction equation

HRID 1888299 reaction equation
C([N-]C(C)C)(C)C.[Li+].[Si:9]([O:16][CH2:17][C@H:18]1[CH2:22][CH2:21][C:20](=[O:23])[N:19]1[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10].C1([Se]Cl)C=CC=CC=1.[Cl-].[NH4+]>O1CCCC1>[Si:9]([O:16][CH2:17][C@H:18]1[CH:22]=[CH:21][C:20](=[O:23])[N:19]1[C:24]([O:26][C:27]([CH3:30])([CH3:29])[CH3:28])=[O:25])([C:12]([CH3:15])([CH3:14])[CH3:13])([CH3:11])[CH3:10]

Participants

6

Reactant 4

HCID 21928ChloroselenobenzeneHCID 25517Ammonium ChlorideHCID 2724682Lithium diisopropylamideHCID 13195229HCID 13195229, compound

Product 1

HCID 11012861HCID 11012861, compoundYield 28.9%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

Lithium diisopropylamide (2M solution in heptane/tetrahydrofuran/ethylbenzene) solution (11.98 mL) was added dropwise slowly to a solution of the compound 11 (6.58 g) in tetrahydrofuran (15 mL) and the solution was stirred at 30 minutes. A solution of Benzeneselenenyl chloride (4.59 g) in tetrahydrofuran (30 mL) was added dropwise slowly to the reaction solution, which was stirred at −78° C. for 1 hour. To the reaction solution was added an aqueous saturated ammonium chloride solution at −78° C. The reaction solution was extracted with ethyl acetate. The organic layer was washed with brine and dried over anhydrous magnesium sulfate. The reaction solution was filtrated through Celite (Brand name) and concentrated. The obtained residue was purified by flush column chromatography (n-hexane:ethyl acetate=20:1). To a solution of the obtained compound (3.87 g) in tetrahydrofuran/ethyl acetate (2:3) (80 mL) were added sodium bicarbonate (1.68 g) and 30% hydrogen peroxide solution (3.2 mL) at 0° C. After 1 hour, to the reaction mixture was added water. The reaction solution was extracted with ethyl acetate. The organic layer was washed with an aqueous saturated sodium bicarbonate solution and brine, and dried over anhydrous magnesium sulfate. The reaction solution was filtrated through Celite (Brand name) and concentrated. The obtained residue was purified by flush column chromatography (n-hexane:ethyl acetate=15:1) to give the title compound (1.89 g) having the following physical data.

Workup

  1. stirringwas stirred at −78° C. for 1 hour
  2. extractionThe reaction solution was extracted with ethyl acetate
  3. washThe organic layer was washed with brine
  4. dry with materialdried over anhydrous magnesium sulfate
  5. filtrationThe reaction solution was filtrated through Celite (Brand name)
  6. concentrationconcentrated
  7. customThe obtained residue was purified
  8. customby flush column chromatography (n-hexane:ethyl acetate=20:1)
  9. additionTo a solution of the obtained compound (3.87 g) in tetrahydrofuran/ethyl acetate (2:3) (80 mL) were added sodium bicarbonate (1.68 g) and 30% hydrogen peroxide solution (3.2 mL) at 0° C
  10. waitAfter 1 hour
  11. additionto the reaction mixture was added water
  12. extractionThe reaction solution was extracted with ethyl acetate
  13. washThe organic layer was washed with an aqueous saturated sodium bicarbonate solution and brine
  14. dry with materialdried over anhydrous magnesium sulfate
  15. filtrationThe reaction solution was filtrated through Celite (Brand name)
  16. concentrationconcentrated
  17. customThe obtained residue was purified
  18. customby flush column chromatography (n-hexane:ethyl acetate=15:1)

Sources & evidence

ORD record
ord-f4a56d5135194eedad351de897859cc1
Source dataset
uspto-grants-2013_08
Patent number
US08501793B2

Reaction notes

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