Carbon tetrabromide → 3-(Bromomethyl)-2-fluoropyridine

HRID 1625068Notes

Reaction equation

HRID 1625068 reaction equation
[F:1][C:2]1[C:7]([CH2:8]O)=[CH:6][CH:5]=[CH:4][N:3]=1.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.C(Br)(Br)(Br)[Br:30]>C(Cl)Cl>[Br:30][CH2:8][C:7]1[C:2]([F:1])=[N:3][CH:4]=[CH:5][CH:6]=1

Participants

5

Reactant 3

HCID 11205Carbon tetrabromide2×HCID 11776Triphenylphosphine2×HCID 147614612-Fluoro-3-(hydroxymethyl)pyridine

Product 1

HCID 230708853-(Bromomethyl)-2-fluoropyridineYield 107.6%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Procedure

To a solution of (2-fluoro-3-pyridinyl)methanol (ASYNCHEM, 505 mg, 3.97 mmol) in dry DCM (15 mL), under N2 atmosphere, were added triphenylphospine (ALDRICH, 1042 mg, 3.97 mmol) and carbon tetrabromide (ALDRICH, 1318 mg, 3.97 mmol) in an ice-water bath. Reaction mixture was stirred at room temperature overnight. 0.3 eq. of carbon tetrabromide (ALDRICH, 409 mg, 1.19 mmol) and 0.3 eq. of triphenylphospine (ALDRICH, 323 mg, 1.19 mmol) were added. Reaction mixture was stirred until starting material was not detected. Solvent was evaporated to dryness. Residue was purified by silica gel chromatography using a linear gradient of hexane-EtOAc. Collected fractions afforded title compound (812 mg, 4.27 mmol, quantitative yield) as yellow oil. 1H NMR (300 MHz, DMSO-d6) δ ppm: 8.20-8.21 (m, 1H), 8.06-8.12 (m, 1H), 735-7.39 (m, 1H), 4.69 (s, 2H). [ES+MS] m/z 190 (M).

Workup

  1. customReaction mixture
  2. customReaction mixture
  3. stirringwas stirred
  4. customSolvent was evaporated to dryness
  5. customResidue was purified by silica gel chromatography

Sources & evidence

ORD record
ord-33203c28d67c46c2a8c567b967ce32e8
Source dataset
uspto-grants-2014_07
Patent number
US08779153B2

Reaction notes

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