Lithium diisopropylamide → 2-Chloro-3-(2,2-dipyridin-3-ylethyl)pyridine

HRID 1686069Notes

Reaction equation

HRID 1686069 reaction equation
[N:1]1[CH:6]=[CH:5][CH:4]=[C:3]([CH2:7][C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[CH:2]=1.[Li+].CC([N-]C(C)C)C.Br[CH2:23][C:24]1[C:25]([Cl:30])=[N:26][CH:27]=[CH:28][CH:29]=1>C1COCC1>[Cl:30][C:25]1[C:24]([CH2:23][CH:7]([C:8]2[CH:9]=[N:10][CH:11]=[CH:12][CH:13]=2)[C:3]2[CH:2]=[N:1][CH:6]=[CH:5][CH:4]=2)=[CH:29][CH:28]=[CH:27][N:26]=1

Participants

5

Reactant 3

HCID 2724682Lithium diisopropylamideHCID 147626403,3'-MethylenedipyridineHCID 189310283-(Bromomethyl)-2-chloropyridine

Product 1

HCID 866343192-Chloro-3-(2,2-dipyridin-3-ylethyl)pyridine

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Procedure

A solution of bis-(3-pyridyl)methane in 150 mL of THF was cooled to −30 C. LDA (1.5 M solution in cyclohexane, 29.4 mL) was added dropwise to give a dark red solution containing some red solid matter. The mixture was then stirred at 0 C for 10 min. A solution of 3-(bromomethyl)-2-chloropyridine in 50 mL of THF was added dropwise over 25 min, and the reaction was stirred at 0 C for 2 h, after which the reaction was quenched by adding saturated aqueous NH4Cl. The mixture was partitioned between saturated aqueous sodium bicarbonate and CH2Cl2. The aqueous solution was extracted with CH2Cl2 (3×), and the combined organic solutions were dried (Na2SO4) and concentrated. Flash chromatography gave 9.1 g of 2-chloro-3-(2,2-dipyridin-3-ylethyl)pyridine as a red, viscous liquid.

Workup

  1. customto give a dark red solution
  2. additioncontaining some red solid matter
  3. stirringthe reaction was stirred at 0 C for 2 h
  4. customafter which the reaction was quenched
  5. additionby adding saturated aqueous NH4Cl
  6. customThe mixture was partitioned between saturated aqueous sodium bicarbonate and CH2Cl2
  7. extractionThe aqueous solution was extracted with CH2Cl2 (3×)
  8. dry with materialthe combined organic solutions were dried (Na2SO4)
  9. concentrationconcentrated

Sources & evidence

ORD record
ord-aa795bb8d0104db68904c84d988e479a
Source dataset
uspto-grants-2012_04
Patent number
US08148535B2

Reaction notes

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