Water → Pyridine, 2-fluoro-4-(1-pentynyl)- (9CI)

HRID 859963Notes

Reaction equation

HRID 859963 reaction equation
[F:1][C:2]1[CH:7]=[C:6](I)[CH:5]=[CH:4][N:3]=1.C(N(CC)CC)C.[CH:16]#[C:17][CH2:18][CH2:19][CH3:20].O>O1CCCC1.[Cu]I.CCOCC>[F:1][C:2]1[CH:7]=[C:6]([C:16]#[C:17][CH2:18][CH2:19][CH3:20])[CH:5]=[CH:4][N:3]=1

Participants

8

Reactant 4

HCID 962WaterHCID 8471TriethylamineHCID 123091-PentyneHCID 70235702-Fluoro-4-iodopyridine

Product 1

HCID 45090791Pyridine, 2-fluoro-4-(1-pentynyl)- (9CI)Yield 92%

Reagents, catalysts & solvents 3

HCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 3283Diethyl EtherSolventHCID 8028TetrahydrofuranSolvent

Procedure

To a cold (0° C.) solution of 2-fluoro-4-iodopyridine (1.0 g, 4.5 mmol) in tetrahydrofuran (15 mL) was added copper (I) iodide (86 mg, 0.45 mmol), dichlorobistriphenylphosphine palladium (II) (157 mg, 0.22 mmol), and triethylamine (1.8 mL, 13.4 mmol). Pentyne (0.88 mL, 8.9 mmol) was added dropwise to the reaction mixture and the resultant solution was stirred at 0° C. for 30 minutes and then at room temperature for 18 hours. Water and ether were added and the layers separated. The organic layer was washed with brine. The aqueous layer was extracted with ether and the combined organics were dried over magnesium sulfate. Filtration and concentration followed flash chromatography on silica gel (5:1 hexane-ether) provided 2-fluoro-4-pent-1-ynylpyridine (670 mg, 92%) as a clear oil. 1H NMR (CDCl3) δ 8.11 (d, 1H), 7.11 (d, 1H), 6.88 (s, 1H), 2.41 (t, 2H), 1.63 (m, 2H), 1.04 (t,3H),; 19F NMR (CDCl3) δ −68.68; MS m/z 164 (M+1).

Workup

  1. customthe layers separated
  2. washThe organic layer was washed with brine
  3. extractionThe aqueous layer was extracted with ether
  4. dry with materialthe combined organics were dried over magnesium sulfate
  5. filtrationFiltration and concentration

Sources & evidence

ORD record
ord-e4d9ae62287e4001aa1481f62cfb03f2
Source dataset
uspto-grants-2006_12
Patent number
US07153863B2

Reaction notes

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