Triphenylphosphine → Methyl [3-(3-bromopropoxy)phenyl]acetate

HRID 1296959Notes

Reaction equation

[OH:1][C:2]1[CH:3]=[C:4]([CH2:8][C:9]([O:11][CH3:12])=[O:10])[CH:5]=[CH:6][CH:7]=1.[Br:13][CH2:14][CH2:15][CH2:16]O.C1(P(C2C=CC=CC=2)C2C=CC=CC=2)C=CC=CC=1.CC(OC(/N=N/C(OC(C)C)=O)=O)C>C1(C)C=CC=CC=1.CCCCCC>[Br:13][CH2:14][CH2:15][CH2:16][O:1][C:2]1[CH:3]=[C:4]([CH2:8][C:9]([O:11][CH3:12])=[O:10])[CH:5]=[CH:6][CH:7]=1

Participants

Conditions

Temperature: 0 °C

Procedure

A solution of methyl 3-hydroxyphenylacetate (11.3 g, 0.068 mole) in 300 mL of anhydrous toluene was treated with 3-bromopropanol (12.2 g, 0.088 mole). Polymer bound triphenylphosphine (36.0 g, 0.108 mole, 3 mmol/g, Fluka Chemie) was then added, and the mixture reacted for 15 minutes. The reaction mixture was then cooled to 0° C. and diisopropylazodicarboxylate (16.9 g, 0.084 mol) was added in a dropwise fashion. After stirring at room temperature overnight, the crude reaction mixture was filtered and the solid washed with 100 mL toluene. After concentration of the filtrate in vacuo, the crude product was purified by column chromatography over silica gel (silica gel 60, EM Science) using 15% EtOAc:hexane as eluent to afford 15.8 g (81% yield) of the title compound as an oil: 1H NMR (CDCl3, 400 MHz) δ 7.23–7.19 (m, 1 H), 6.85–6.7 (m, 3), 4.09–4.06 (t, 2 H, J=5.8), 3.67 (s, 3 H), 3.67–3.56 (m, 4 H), 2.32–2.26 (p, 2 H, J=6.0); MS (ESP+) m/e 288 (MH+); TLC (hexanes:EtOAc/3:1) Rf=0.68. Anal. (C12H15O3Br) C, H, N.

Workup

additionwas then added
customthe mixture reacted for 15 minutes
customthe crude reaction mixture
filtrationwas filtered
washthe solid washed with 100 mL toluene
customAfter concentration of the filtrate in vacuo, the crude product was purified by column chromatography over silica gel (silica gel 60, EM Science)

Sources & evidence

ORD record: ord-591a7ead320c4181b31f66715adfca49
Source dataset: uspto-grants-2007_07
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07247748B2

Reaction notes

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