Methyl 2-(4-bromophenyl)acetate → 4-(3-Hydroxyprop-2-ynyl)phenylacetic acid methyl ester

HRID 484452Notes

Reaction equation

HRID 484452 reaction equation
[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8](Br)=[CH:7][CH:6]=1.[C:13]([OH:16])#[C:14][CH3:15]>C(N(CC)CC)C.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.Cl[Pd]Cl>[CH3:1][O:2][C:3](=[O:12])[CH2:4][C:5]1[CH:10]=[CH:9][C:8]([CH2:15][C:14]#[C:13][OH:16])=[CH:7][CH:6]=1

Participants

5

Reactant 2

HCID 316783Methyl 2-(4-bromophenyl)acetateHCID 6432594Prop-1-yn-1-ol

Product 1

HCID 676914574-(3-Hydroxyprop-2-ynyl)phenylacetic acid methyl esterYield 27.4%

Reagents, catalysts & solvents 2

HCID 6102075Dichlorobis(triphenylphosphine)palladiumCatalystHCID 8471TriethylamineSolvent

Conditions

Temperature
65 °C

Procedure

4-Bromophenylacetic acid methyl ester (23 g, 0.1 mol) was dissolved in dry triethylamine (80 ml) with propynol (5.82 ml, 0.1 mol). After the addition of cuprous iodide (0.3 g) and bis (triphenylphosphine)palladium (II) chloride (1 g) the reaction mixture was heated at 65° C. under nitrogen for 14 h. The solvent was evaporated under vacuum and the residue was dissolved in ethyl acetate (500 ml) and washed successively with 0.5M citric acid solution (2×200 ml), saturated sodium hydrogen carbonate solution (2×200 ml) and brine (1×150 ml). The organic solution was dried (Na2SO4), filtered and concentrated in vacuo to give an oil which was purified by chromatography on silica gel using 20% ethyl acetate in hexane as eluent to give the required compound (5.6 g) as an oil. δ (360 MHz, CDCl3) 3.62 (2H, s, CH2CO2CH3), 3.69 (3H, s, CH2CO2CH3), 4.48 (1H, s, HOCH2), 7.22 (2H, d, J=8.2 Hz, ArH), 7.39 (2H, d, J=8.2 Hz, ArH); m/e 204 (M+).

Workup

  1. customThe solvent was evaporated under vacuum
  2. dissolutionthe residue was dissolved in ethyl acetate (500 ml)
  3. washwashed successively with 0.5M citric acid solution (2×200 ml), saturated sodium hydrogen carbonate solution (2×200 ml) and brine (1×150 ml)
  4. dry with materialThe organic solution was dried (Na2SO4)
  5. filtrationfiltered
  6. concentrationconcentrated in vacuo
  7. customto give an oil which
  8. customwas purified by chromatography on silica gel using 20% ethyl acetate in hexane as eluent

Sources & evidence

ORD record
ord-a954e136a768481dbfbccea515792343
Source dataset
uspto-grants-1993_07
Patent number
US05231102

Reaction notes

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