Acetic Acid → 3-(Bromomethyl)pyridine-2-carbonitrile

HRID 1784181Notes

Reaction equation

HRID 1784181 reaction equation
[CH3:1][C:2]1[C:3]([C:8]#[N:9])=[N:4][CH:5]=[CH:6][CH:7]=1.[Br:10]N1C(=O)CCC1=O.CC(O)=O.CC(N=NC(C#N)(C)C)(C#N)C>C(Cl)(Cl)(Cl)Cl>[Br:10][CH2:1][C:2]1[C:3]([C:8]#[N:9])=[N:4][CH:5]=[CH:6][CH:7]=1

Participants

6

Reactant 4

HCID 176Acetic AcidHCID 6547AzobisisobutyronitrileHCID 67184N-bromobutanimideHCID 8199283-Methylpyridine-2-carbonitrile

Product 1

HCID 103754503-(Bromomethyl)pyridine-2-carbonitrileYield 21.4%

Reagents, catalysts & solvents 1

HCID 5943Carbon TetrachlorideSolvent

Procedure

To a solution of 3-methylpicolinonitrile (700 mg, 5.93 mmol) in CCl4 (15 mL) was added recrystallized N-bromosuccinimide (1.21 g, 6.82 mmol), followed by glacial HOAc (0.34 mL, 1.0 eq), and AIBN (97 mg, 0.60 mmol). The resultant mixture was heated to 65° C. for 3 hours, 80° C. for 2 hours, and then cooled to room temperature. The mixture was filtered through filter paper, and the filtrate was concentrated. Purification of the crude material by flash chromatography (Hexanes/EtOAc, 90:10 followed by 80:20) provided 3-bromomethyl-pyridine-2-carbonitrile (250 mg, 21%) as a white solid. 1H NMR (CDCl3) δ 4.63 (s, 2H), 7.55 (dd, 1H, J=8.0, 4.6 Hz), 7.93 (dd, 1H, J=7.9, 1.2 Hz), 8.64 (dd, 1H, J=4.8, 1.4 Hz).

Workup

  1. filtrationThe mixture was filtered
  2. filtrationthrough filter paper
  3. concentrationthe filtrate was concentrated
  4. customPurification of the crude material by flash chromatography (Hexanes/EtOAc, 90:10 followed by 80:20)

Sources & evidence

ORD record
ord-798af5c23b554ecd94e682f9b9a291b4
Source dataset
uspto-grants-2009_03
Patent number
US07501518B2

Reaction notes

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