Propargyl alcohol → 3-(2-Fluorophenyl)prop-2-yn-1-ol

HRID 1837940Notes

Reaction equation

HRID 1837940 reaction equation
[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1I.[CH2:9]([OH:12])[C:10]#[CH:11]>CCN(CC)CC.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.C1C=CC(P(C2C=CC=CC=2)[C-]2C=CC=C2)=CC=1.Cl[Pd]Cl.[Fe+2].[Cu]I.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[F:1][C:2]1[CH:7]=[CH:6][CH:5]=[CH:4][C:3]=1[C:11]#[C:10][CH2:9][OH:12]

Participants

7

Reactant 2

HCID 7859Propargyl alcoholHCID 676731-Fluoro-2-iodobenzene

Product 1

HCID 27826963-(2-Fluorophenyl)prop-2-yn-1-olYield 87%

Reagents, catalysts & solvents 4

HCID 11776TriphenylphosphineCatalystHCID 24350Copper(1+) iodide; Copper(I) iodide; Cuprous iodide; Cuprous iodide (CuI)CatalystHCID 178418228Bis(cyclopenta-1,4-dien-1-yl(diphenyl)phosphane);dichloropalladium;iron(2+)CatalystHCID 8471TriethylamineSolvent

Procedure

To a solution of 2-fluoro-iodobenzene (267 g, 1.2 mol) in Et3N (6L) was added propargyl alcohol (140 g, 2.5 mol, 2 equiv), followed by PdCl2(dppf) (6.1 g, 8.8 mmol, 0.007 equiv), Ph3P (12.5 g, 47.6 mmol, 0.038 equiv) and copper(I) iodide (12.6 g, 66.3 mmol, 0.053 equiv). The resulting mixture was heated at the reflux temperature for 17 h, allowed to cool to room temperature and filtered through a pad of Celite®. The filtrate was concentrated under reduced pressure and purified by vacuum distillation to give 3-(2-fluorophenyl)prop-2-yn-1-ol (156.6 g, 87%) as a deep brown oil: bp 84° C./0.3 mmHg; TLC (CH2Cl2) Rf 0.44; 1H NMR (CDCl3) δ 2.46 (d, J=5.0 Hz, 1H), 4.45 (d, J=5.0 Hz, 1H), 6.94-7.02 (m, 2H), 7.17-7.23 (m, 1H), 7.31-7.37 (m, 1H); GCMS m/z (rel abundance) 151 (MH+, 75%).

Workup

  1. temperatureThe resulting mixture was heated at the reflux temperature for 17 h
  2. filtrationfiltered through a pad of Celite®
  3. concentrationThe filtrate was concentrated under reduced pressure
  4. distillationpurified by vacuum distillation

Sources & evidence

ORD record
ord-0e26c05cfb2046568b618137b75d6628
Source dataset
uspto-grants-2004_08
Patent number
US06784167B2

Reaction notes

Loading…