2,5-Dibromo-3-methylpyridine → HCID 86692466, compound

HRID 1748517Notes

Reaction equation

HRID 1748517 reaction equation
C[Si]([N-][Si](C)(C)C)(C)C.[Na+].[O:11]1[C:15]2([CH2:20][CH2:19][CH:18]([C:21]#[N:22])[CH2:17][CH2:16]2)OCC1.Br[C:24]1[C:29]([CH3:30])=[CH:28][C:27]([Br:31])=[CH:26][N:25]=1>O>[Br:31][C:27]1[CH:28]=[C:29]([CH3:30])[C:24]([C:18]2([C:21]#[N:22])[CH2:17][CH2:16][C:15](=[O:11])[CH2:20][CH2:19]2)=[N:25][CH:26]=1

Participants

5

Reactant 3

HCID 8176802,5-Dibromo-3-methylpyridineHCID 2724254Sodium bis(trimethylsilyl)amideHCID 111164331,4-Dioxaspiro[4.5]decane-8-carbonitrile

Product 1

HCID 86692466HCID 86692466, compoundYield 97.6%

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Procedure

1M Solution of sodium bis(trimethylsilyl)amide (77 ml) was added under ice cooling to 1,4-dioxaspiro[4,5]decane-8-carbonitrile (11.0 g) described in Reference Example 82(1) and stirred for 30 minutes. Then, 2,5-dibromo-3-methylpyridine (15 g) was added, stirred for 30 minutes and further stirred at room temperature for an hour. The reaction solution was treated with water and extracted with ethyl acetate. The organic layer was washed with saturated brine and concentrated in vacuo. To the residue, were added trifluoroacetic acid (20 ml) and water (5 ml), and the mixture was stirred at 40° C. for two hours. The reaction solution was treated with an aqueous solution of sodium carbonate and extracted with ethyl acetate. The organic layer was dried over anhydrous magnesium sulfate, concentrated in vacuo and the residue was purified with silica gel column chromatography (ethyl acetate:n-hexane=5:1) to give 1-(5-bromo-3-methylpyridin-2-yl)-4-oxocyclohexanecarbonitrile (17.1 g).

Workup

  1. stirringstirred for 30 minutes
  2. stirringfurther stirred at room temperature for an hour
  3. extractionextracted with ethyl acetate
  4. washThe organic layer was washed with saturated brine
  5. concentrationconcentrated in vacuo
  6. additionTo the residue, were added trifluoroacetic acid (20 ml) and water (5 ml)
  7. stirringthe mixture was stirred at 40° C. for two hours
  8. additionThe reaction solution was treated with an aqueous solution of sodium carbonate
  9. extractionextracted with ethyl acetate
  10. dry with materialThe organic layer was dried over anhydrous magnesium sulfate
  11. concentrationconcentrated in vacuo
  12. customthe residue was purified with silica gel column chromatography (ethyl acetate:n-hexane=5:1)

Sources & evidence

ORD record
ord-e4117e1006d04953b51817983f401cf9
Source dataset
uspto-grants-2015_10
Patent number
US09150555B2

Reaction notes

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