Potassium Cyanide → 2-(6-Bromopyridin-3-yl)acetonitrile

HRID 1614364Notes

Reaction equation

HRID 1614364 reaction equation
[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8]Br)=[CH:4][N:3]=1.[C-:10]#[N:11].[K+]>CN(C)C=O>[Br:1][C:2]1[CH:7]=[CH:6][C:5]([CH2:8][C:10]#[N:11])=[CH:4][N:3]=1

Participants

4

Reactant 2

HCID 9032Potassium CyanideHCID 64246602-Bromo-5-bromomethylpyridine

Product 1

HCID 177499762-(6-Bromopyridin-3-yl)acetonitrileYield 32%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent

Procedure

The 476 g of crude 2-bromo-5-bromomethylpyridine from step 4 was dissolved in 4000 mL of dimethylformamide (DMF)/water (7:1) and treated with 168 g (2.58 mol) of potassium cyanide. The reaction was allowed to stir at ambient temperature for 72 h, concentrated in vacuo, and partitioned between ethyl acetate and water; the organic layer was washed with water, washed with brine, dried (MgSO4), and reconcentrated in vacuo to provide the crude nitrile. Purification by silica gel chromatography (Waters Prep-500A) using ethyl acetate/hexane (25:75) gave 109 g (32% from 2-bromo-5-picoline) of 2-bromo-5-cyanomethylpyridine as a yellowish orange solid: mp 55.5°-57.5° C.; NMR (CDCl3)δ3.74 (s, 2 H), 7.54 (d, J=8 Hz, 1 H), 7.59 (dd, J=8 and 2 HZ, 1 H), 8.35 (d, J=2 Hz, 1 H); MS (FAB) m/e (rel intensity) 199 (85), 197 (100).

Workup

  1. concentrationconcentrated in vacuo
  2. custompartitioned between ethyl acetate and water
  3. washthe organic layer was washed with water
  4. washwashed with brine
  5. dry with materialdried (MgSO4)
  6. customto provide the crude nitrile
  7. customPurification by silica gel chromatography (Waters Prep-500A)

Sources & evidence

ORD record
ord-79362656e88042f9be2cab5b67d2175c
Source dataset
uspto-grants-1993_03
Patent number
US05196537

Reaction notes

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