3-Bromopyridine → HCID 24822234, compound

HRID 2399667Notes

Reaction equation

HRID 2399667 reaction equation
[Li]CCCC.Br[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1.Cl[Si:14]([CH3:22])([CH3:21])[C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1>CCOCC>[CH3:21][Si:14]([CH3:22])([C:15]1[CH:20]=[CH:19][CH:18]=[CH:17][CH:16]=1)[C:7]1[CH:8]=[N:9][CH:10]=[CH:11][CH:12]=1

Participants

5

Reactant 3

HCID 122863-BromopyridineHCID 13029ChlorodimethylphenylsilaneHCID 178418339Butyllithium

Product 1

HCID 24822234HCID 24822234, compoundYield 31.2%

Reagents, catalysts & solvents 1

HCID 3283Diethyl EtherSolvent3×

Procedure

In a 1 liter, 4 neck round bottom flask stirring under N2 was charged 80.6 milliliters (ml) of n-BuLi (1.55 Molar (M) solution, 0.125 moles, 1.25 equivalents (eq.)) to 300 ml of ether with stirring at -78° C. To the reaction was added, dropwise, 15.8 grams (g) of 3-bromopyridine (0.10 moles, 1.0 eq.) in 100 ml of ether, over 20 minutes while maintaining the temperature between -50° C. and -70° C. After stirring for 20 minutes, 21.3 g of chlorodimethylphenylsilane (0.125 moles, 1.25 eq.) in 50 ml of ether was added dropwise maintaining the temperature below -50° C. after which the reaction was allowed to come to ambient temperature. After 1 hour, gas liquid chromatography (GLC) indicated complete consumption of the silyl chloride. The reaction mixture was stirred overnight at room temperature. The reaction was quenched by adding 200 ml of water, and extracted with ether/ethyl acetate (200 ml/450 ml) and washed with water (2×200 ml). Drying and concentrating afforded 26.0 g of crude product of which 6.7 g was purified by flash chromatography with 3:7 ethyl acetate/hexane and afforded 2.1 g of an oil (31.2% yield based on the 6.7 g chromatographed portion).

Workup

  1. stirringwith stirring at -78° C
  2. additionTo the reaction was added
  3. stirringAfter stirring for 20 minutes
  4. temperaturemaintaining the temperature below -50° C. after which the reaction
  5. customto come to ambient temperature
  6. customconsumption of the silyl chloride
  7. stirringThe reaction mixture was stirred overnight at room temperature
  8. customThe reaction was quenched
  9. additionby adding 200 ml of water
  10. extractionextracted with ether/ethyl acetate (200 ml/450 ml)
  11. washwashed with water (2×200 ml)
  12. customDrying
  13. concentrationconcentrating
  14. customafforded 26.0 g of crude product of which 6.7 g
  15. customwas purified by flash chromatography with 3:7 ethyl acetate/hexane

Sources & evidence

ORD record
ord-9253da017e274cc7a543e6e6d2311ef5
Source dataset
uspto-grants-1995_09
Patent number
US05451563

Reaction notes

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